40 CFR 59.505 - How do I demonstrate compliance with the reactivity limits?

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) AIR PROGRAMS (CONTINUED) NATIONAL VOLATILE ORGANIC COMPOUND EMISSION STANDARDS FOR CONSUMER AND COMMERCIAL PRODUCTS National Volatile Organic Compound Emission Standards for Aerosol Coatings § 59.505 How..., 2B, or 2C. WFi = weight fraction of component i in the product, (2) Calculate the PWR of each product...

CHARACTERIZATION OF FINE PARTICLE ASSOCIATED ORGANIC COMPOUNDS: INTERLABORATORY COMPARISON AND DEVELOPMENT OF STANDARD REFERENCE MATERIALS

EPA Science Inventory

Organic chemicals adsorbed to fine particulate matter (PM) in the ambient air account for a major component of the mass and include source tracers as well as toxic compounds that may contribute to adverse human health effects. The US EPA has established a PM 2.5 research progr...

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

Simoneit, B.R.T.; Radzi bin Abas, M.; Cass, G.R.

Biomass combustion is an important primary source of carbonaceous particles in the global atmosphere. Various molecular markers have been proposed for this process but additional specific tracers are needed. The injection of natural product organic compounds into smoke occurs primarily by direct volatilization/steam stripping and by pyrolysis. Although the composition of organic matter in smoke particles is highly variable, the molecular structures of the tracers are generally source specific. Homologous compounds and biomarkers present in smoke are derived directly from plant wax, gum and resin by volatilization and secondarily from pyrolysis of biopolymers (e.g., lignin, cutin, suberin), wax, gum andmore » resin. The component complexity is illustrated with examples from controlled bums of temperate and tropical biomass fuels. Conifer smoke contains characteristic tracers from diterpenoids as well as phenolics and other oxygenated species. These are recognizable in urban airsheds. The major organic components of smoke from tropical biomass are straight-chain, aliphatic and oxygenated compounds and triterpenoids. Several compounds are potential key indicators for combustion of such biomass. The precursor to product approach of organic geochemistry can be applied successfully to provide molecular tracers for studying smoke plume chemistry and dispersion.« less

Temperature responses of individual soil organic matter components

NASA Astrophysics Data System (ADS)

Feng, Xiaojuan; Simpson, Myrna J.

2008-09-01

Temperature responses of soil organic matter (SOM) remain unclear partly due to its chemical and compositional heterogeneity. In this study, the decomposition of SOM from two grassland soils was investigated in a 1-year laboratory incubation at six different temperatures. SOM was separated into solvent extractable compounds, suberin- and cutin-derived compounds, and lignin-derived monomers by solvent extraction, base hydrolysis, and CuO oxidation, respectively. These SOM components have distinct chemical structures and stabilities and their decomposition patterns over the course of the experiment were fitted with a two-pool exponential decay model. The stability of SOM components was also assessed using geochemical parameters and kinetic parameters derived from model fitting. Compared with the solvent extractable compounds, a low percentage of lignin monomers partitioned into the labile SOM pool. Suberin- and cutin-derived compounds were poorly fitted by the decay model, and their recalcitrance was shown by the geochemical degradation parameter (ω - C16/∑C16), which was observed to stabilize during the incubation. The temperature sensitivity of decomposition, expressed as Q10, was derived from the relationship between temperature and SOM decay rates. SOM components exhibited varying temperature responses and the decomposition of lignin monomers exhibited higher Q10 values than the decomposition of solvent extractable compounds. Our study shows that Q10 values derived from soil respiration measurements may not be reliable indicators of temperature responses of individual SOM components.

On the Complex Coupling Between the Production of Ozone and Secondary Organic Aerosol in Polluted Urban Regions

NASA Astrophysics Data System (ADS)

Stewart, D. R.; Stockwell, W. R.; Morris, V. R.; Fitzgerald, R. M.

2016-12-01

The major photochemical processes that produce ozone and aerosols are coupled together strongly in the polluted urban atmosphere. Aerosols are either directly emitted or formed through the same kind of chemistry that leads to the production of ozone. The aerosols produced through atmospheric chemistry are known as secondary aerosols and they may be composed of inorganic (nitrates, sulfates) or organic compounds. Wind blown dust and soot are two examples of primary aerosols. The component of secondary inorganic aerosols includes compounds such as ammonium nitrate, ammonium bisulfate and ammonium sulfate. Secondary organic aerosols are a very important component of PM with strong implications for health. The formation of secondary organic aerosol is linked with ozone photochemistry through the reactions of volatile organic compounds (VOC). The oxidation of VOC produces radicals that convert nitric oxide to nitrogen dioxide that photolyze to produce ozone. Larger VOC (those with more carbon atoms) undergo a number of oxidation cycles that add oxygen atoms to large organic molecules. The vapor pressure of many of these highly oxidized compounds is sufficiently low that they condense to produce secondary organic aerosols. The Community Multi-scale Air Quality model (CMAQ) and other chemical simulations have been made to quantify the relationship between varying emissions of VOC and NOx and the production of inorganic and secondary organic aerosols. The results from this analysis will be presented.

Assessment of Volatile Organic Compound and Hazardous Air Pollutant Emissions from Oil and Natural Gas Well Pads using Mobile Remote and On-site Direct Measurements

EPA Science Inventory

Emissions of volatile organic compounds (VOC) and hazardous air pollutants (HAP) from oil and natural gas production were investigated using direct measurements of component-level emissions on well pads in the Denver-Julesburg (DJ) Basin and remote measurements of production pad-...

Search for organic and volatile inorganic compounds in two surface samples from the chryse planitia region of Mars.

PubMed

Biemann, K; Oro, J; Toulmin, P; Orgel, L E; Nier, A O; Anderson, D M; Simmonds, P G; Flory, D; Diaz, A V; Rushneck, D R; Biller, J A

1976-10-01

Two surface samples collected from the Chryse Planitia region of Mars were heated to temperatures up to 500 degrees C, and the volatiles that they evolved were analyzed with a gas chromatograph-mass spectrometer. Only water and carbon dioxide were detected. This implies that organic compounds have not accumulated to the extent that individual components could be detected at levels of a few parts in 10(9) by weight in our samples. Proposed mechanisms for the accumulation and destruction of organic compounds are discussed in the light of this limit.

Search for organic and volatile inorganic compounds in two surface samples from the Chryse Planitia region of Mars

NASA Technical Reports Server (NTRS)

Biemann, K.; Oro, J.; Toulmin, P., III; Orgel, L. E.; Nier, A. O.; Anderson, D. M.; Flory, D.; Diaz, A. V.; Rushneck, D. R.; Simmonds, P. G.

1976-01-01

Two surface samples collected from the Chryse Planitia region of Mars were heated to temperatures up to 500 C, and the volatiles that they evolved were analyzed with a gas chromatograph-mass spectrometer. Only water and carbon dioxide were detected. This implies that organic compounds have not accumulated to the extent that individual components could be detected at levels of a few parts per billion by weight in the samples. Proposed mechanisms for the accumulation and destruction of organic compounds are discussed in the light of this limit.

Search for organic and volatile inorganic compounds in two surface samples from the chryse planitia region of Mars

USGS Publications Warehouse

Biemann, K.; Oro, John; Toulmin, P.; Orgel, Leslie E.; Nier, A.O.; Anderson, D.M.; Simmonds, P.G.; Flory, D.; Diaz, A.V.; Rushneck, D.R.; Biller, J.A.

1976-01-01

Two surface samples collected from the Chryse Planitia region of Mars were heated to temperatures up to 500??C, and the volatiles that they evolved were analyzed with a gas chromatograph-mass spectrometer. Only water and carbon dioxide were detected. This implies that organic compounds have not accumulated to the extent that individual components could be detected at levels of a few parts in 109 by weight in our samples. Proposed mechanisms for the accumulation and destruction of organic compounds are discussed in the light of this limit.

Evolution of organic matter in Orgueil, Murchison and Renazzo during parent body aqueous alteration: In situ investigations

NASA Astrophysics Data System (ADS)

Le Guillou, Corentin; Bernard, Sylvain; Brearley, Adrian J.; Remusat, Laurent

2014-04-01

Chondrites accreted the oldest solid materials in the solar system including dust processed in the protoplanetary disk and diverse organic compounds. After accretion, asteroidal alteration may have impacted organic particles in various ways. To constrain these processes, we conducted a comprehensive study of organics disseminated within the matrices of the three carbonaceous chondrite falls, Renazzo (CR2), Murchison (CM2) and Orgueil (CI). By combining synchrotron-based STXM and TEM analyses on FIB sections of samples previously characterized by NanoSIMS, we investigated the influence of aqueous alteration on the morphology, isotopic signature, molecular structure, spatial distribution, and mineralogical environment of the organic matter within the matrices. Two different populations of materials are distinguishable: sub-micrometric individual grains, likely dominated by insoluble compounds and diffuse organic matter, finely interspersed within phyllosilicates and/or (amorphous) nanocarbonates at the nanometer scale. We suggest that this latter component, which is depleted in aromatics and enriched in carboxylic functional groups, may be dominated by soluble compounds. Organic matter in Renazzo (CR) mainly consists of chemically-homogeneous individual grains surrounded by amorphous and nanocrystalline phyllosilicates. Evidence of connectivity between organic grains and fractures indicates that redistribution has occurred: some areas containing diffuse organic matter can be observed. This diffuse organic component is more abundant in Murchison (CM) and Orgueil (CI). This is interpreted as resulting from fluid transport at the micrometer scale and encapsulation within recrystallized alteration phases. In contrast to Renazzo, organic grains in Murchison and Orgueil display strong chemical heterogeneities, likely related to chemical evolution during aqueous alteration. The observations suggest that the altering fluid was a brine with elevated concentrations of both organic and inorganic soluble components. Ultimately, when water was consumed by aqueous alteration reactions or lost from the system, soluble organic compounds accumulated in the immediate vicinity of the precipitated carbonates and phosphates. Additionally, the nanometer scale organic/phyllosilicate relationships provide a petrological environment where some of the initially accreted organic matter could have been modified through clay-mediated reactions.

Water-soluble organic nitrogen in atmospheric fine particles (PM2.5) from northern California

NASA Astrophysics Data System (ADS)

Zhang, Qi; Anastasio, Cort; Jimenez-Cruz, Mike

2002-06-01

Recent studies have suggested that organic nitrogen (ON) is a ubiquitous and significant component of atmospheric dry and wet deposition, but very little is known about the concentrations and speciation of organic nitrogen in aerosol particles. In addition, while amino compounds also appear to be ubiquitous in atmospheric condensed phases, their contribution to organic nitrogen has not been previously quantified. To address these issues, we have characterized the water-soluble organic nitrogen and amino compounds in fine particles (PM2.5) collected in Davis, California, over a period of 1 year. Concentrations of water-soluble organic nitrogen (WSON) ranged from 3.1-57.8 nmol N m-3 air, peaking during winter and early spring, and typically accounted for ~20% of total nitrogen in Davis PM2.5. Assuming an average N-normalized molecular weight of 100 Da per N atom for WSON, particulate organic nitrogen had a median mass concentration of 1.6 μg m-3 air, and typically represented 18% of the total fine particle mass. The average mass of water-soluble ON in Davis PM2.5 was comparable to that of sulfate during the summer, but was significantly higher in winter. Total amino compounds (free plus combined forms) made up a significant portion of particulate organic nitrogen (median value equal to 23%), primarily due to the presence of combined amino compounds such as proteins and peptides. Total amino compounds had a median mass concentration of 290 ng m-3 air, and typically accounted for 3.3% of the total fine particle mass. These results indicate that organic nitrogen is a significant component of fine particles in northern California, and suggest that this group of compounds might play an important role in the ecological, radiative, and potential health effects of atmospheric fine particles in this region.

Heat detection and compositions and devices therefor

NASA Technical Reports Server (NTRS)

Rembaum, A. (Inventor)

1975-01-01

Temperature change of a substrate such as a microelectronic component is sensed and detected by means of a mixture of a weak molecular complex of an electron donor compound such as an organic amine and an electron acceptor compound such as nitroaromatic compound. The mixture is encapsulated in a clear binder such as a vinyl resin.

Light Absorption and Excitation-Emission Fluorescence of Urban Organic Aerosol Components and Their Relationship to Chemical Structure.

PubMed

Chen, Qingcai; Ikemori, Fumikazu; Mochida, Michihiro

2016-10-18

The present study used a combination of solvent and solid-phase extractions to fractionate organic compounds with different polarities from total suspended particulates in Nagoya, Japan, and their optical characteristics were obtained on the basis of their UV-visible absorption spectra and excitation-emission matrices (EEMs). The relationship between their optical characteristics and chemical structures was investigated based on high-resolution aerosol mass spectra (HR-AMS spectra), soft ionization mass spectra and Fourier transform infrared (FT-IR) spectra. The major light-absorption organics were less polar organic fractions, which tended to have higher mass absorption efficiencies (MAEs) and lower wavelength dependent Ångström exponents (Å) than the more polar organic fractions. Correlation analyses indicate that organic compounds with O and N atoms may contribute largely to the total light absorption and fluorescence of the organic aerosol components. The extracts from the aerosol samples were further characterized by a classification of the EEM profiles using a PARAFAC model. Different fluorescence components in the aerosol organic EEMs were associated with specific AMS ions and with different functional groups from the FT-IR analysis. These results may be useful to determine and further classify the chromophores in atmospheric organic aerosols using EEM spectroscopy.

Isolation of Purines and Pyrimidines from the Murchison Meteorite Using Sublimation

NASA Technical Reports Server (NTRS)

Glavin, D. P.; Bada, J. L.

2004-01-01

The origin of life on Earth, and possibly on other planets such as Mars, would have required the presence of liquid water and a continuous supply of prebiotic organic compounds. The exogenous delivery of organic matter by asteroids, comets, and carbonaceous meteorites could have contributed to the early Earth s prebiotic inventory by seeding the planet with biologically important organic compounds. A wide variety of prebiotic organic compounds have previously been detected in the Murchison CM type carbonaceous chondrite including amino acids, purines and pyrimidines. These compounds dominate terrestrial biochemistry and are integral components of proteins, DNA and RNA. Several purines including adenine, guanine, hypoxanthine, and xanthine, as well as the pyrimidine uracil, have previously been detected in water or formic acid extracts of Murchison using ion-exclusion chromatography and ultraviolet spectroscopy. However, even after purification of these extracts, the accurate identification and quantification of nucleobases is difficult due to interfering UV absorbing compounds. In order to reduce these effects, we have developed an extraction technique using sublimation to isolate purines and pyrimidines from other non-volatile organic compounds in Murchison acid extracts.

Evaluating the mutagenic potential of aerosol organic compounds using informatics-based screening

NASA Astrophysics Data System (ADS)

Decesari, Stefano; Kovarich, Simona; Pavan, Manuela; Bassan, Arianna; Ciacci, Andrea; Topping, David

2018-02-01

Whilst general policy objectives to reduce airborne particulate matter (PM) health effects are to reduce exposure to PM as a whole, emerging evidence suggests that more detailed metrics associating impacts with different aerosol components might be needed. Since it is impossible to conduct toxicological screening on all possible molecular species expected to occur in aerosol, in this study we perform a proof-of-concept evaluation on the information retrieved from in silico toxicological predictions, in which a subset (N = 104) of secondary organic aerosol (SOA) compounds were screened for their mutagenicity potential. An extensive database search showed that experimental data are available for 13 % of the compounds, while reliable predictions were obtained for 82 %. A multivariate statistical analysis of the compounds based on their physico-chemical, structural, and mechanistic properties showed that 80 % of the compounds predicted as mutagenic were grouped into six clusters, three of which (five-membered lactones from monoterpene oxidation, oxygenated multifunctional compounds from substituted benzene oxidation, and hydroperoxides from several precursors) represent new candidate groups of compounds for future toxicological screenings. These results demonstrate that coupling model-generated compositions to in silico toxicological screening might enable more comprehensive exploration of the mutagenic potential of specific SOA components.

Secondary organic aerosol formation from fossil fuel sources contribute majority of summertime organic mass at Bakersfield

EPA Science Inventory

Secondary organic aerosols (SOA), known to form in the atmosphere from oxidation of volatile organic compounds (VOCs) emitted by anthropogenic and biogenic sources, are a poorly understood but substantial component of atmospheric particles. In this study, we examined the chemic...

Optoelectronic devices incorporating fluoropolymer compositions for protection

DOEpatents

Chen, Xuming; Chum, Pak-Wing S.; Howard, Kevin E.; Lopez, Leonardo C.; Sumner, William C.; Wu, Shaofu

2015-12-22

The fluoropolymer compositions of the present invention generally incorporate ingredients comprising one or more fluoropolymers, an ultraviolet light protection component (hereinafter UV protection component), and optionally one or more additional ingredients if desired. The UV protection component includes a combination of at least one hindered tertiary amine (HTA) compound having a certain structure and a weight average molecular weight of at least 1000. This tertiary amine is used in combination with at least one organic, UV light absorbing compound (UVLA compound) having a weight average molecular weight greater than 500. When the HTA compound and the UVLA compound are selected according to principles of the present invention, the UV protection component provides fluoropolymer compositions with significantly improved weatherability characteristics for protecting underlying materials, features, structures, components, and/or the like. In particular, fluoropolymer compositions incorporating the UV protection component of the present invention have unexpectedly improved ability to resist blackening, coloration, or other de gradation that may be caused by UV exposure. As a consequence, devices protected by these compositions would be expected to have dramatically improved service life. The compositions have a wide range of uses but are particularly useful for forming protective layers in optoelectronic devices.

Hygroscopic properties of internally mixed particles composed of NaCl and water-soluble organic acids.

PubMed

Ghorai, Suman; Wang, Bingbing; Tivanski, Alexei; Laskin, Alexander

2014-02-18

Atmospheric aging of naturally emitted marine aerosol often leads to formation of internally mixed particles composed of sea salts and water-soluble organic compounds of anthropogenic origin. Mixing of sea salt and organic components has profound effects on the evolving chemical composition and hygroscopic properties of the resulted particles, which are poorly understood. Here, we have studied chemical composition and hygroscopic properties of laboratory generated NaCl particles mixed with malonic acid (MA) and glutaric acid (GA) at different molar ratios using micro-FTIR spectroscopy, atomic force microscopy, and X-ray elemental microanalysis. Hygroscopic properties of internally mixed NaCl and organic acid particles were distinctly different from pure components and varied significantly with the type and amount of organic compound present. Experimental results were in a good agreement with the AIM modeling calculations of gas/liquid/solid partitioning in studied systems. X-ray elemental microanalysis of particles showed that Cl/Na ratio decreased with increasing organic acid component in the particles with MA yielding lower ratios relative to GA. We attribute the depletion of chloride to the formation of sodium malonate and sodium glutarate salts resulted by HCl evaporation from dehydrating particles.

Hygroscopic Properties of Internally Mixed Particles Composed of NaCl and Water-Soluble Organic Acids

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

Ghorai, Suman; Wang, Bingbing; Tivanski, Alexei V.

Atmospheric aging of naturally emitted marine aerosol often leads to formation of internally mixed particles composed of sea salts and water soluble organic compounds of anthropogenic origin. Mixing of sea salt and organic components has profound effects on the evolving chemical composition and hygroscopic properties of the resulted particles, which are poorly understood. Here, we have studied chemical composition and hygroscopic properties of laboratory generated NaCl particles mixed with malonic acid (MA) and glutaric acid (GA) at different molar ratios using micro-FTIR spectroscopy and X-ray elemental microanalysis.Hygroscopic properties of inte rnally mixed NaCl and organic acid particles were distinctly differentmore » from pure components and varied significantly with the type and amount of organic compound present. Experimental results were in a good agreement with the AIM modeling calculations of gas/liquid/solid partitioning in studied systems. X-ray elemental microanalysis of particles showed that Cl/Na ratio decreased with increasing organic acid component in the particles with MA yielding lower ratios relative to GA. We attribute the depletion of chloride to the formation of Na-malonate and Na-glutarate salts resulted by HCl evaporation from dehydrating particles.« less

Organic Nitrogen in Atmospheric Drops and Particles: Concentrations, (Limited) Speciation, and Chemical Transformations

NASA Astrophysics Data System (ADS)

Anastasio, C.; Zhang, Q.

2003-12-01

While quite a bit is known of the concentrations, speciation, and chemistry of inorganic forms of nitrogen in the atmosphere, the same cannot be said for organic forms. Despite this, there is growing evidence that organic N (ON) is ubiquitous in the atmosphere, especially in atmospheric condensed phases such as fog/cloud drops and aerosol particles. Although the major compounds that make up organic N are generally unknown, as are the sources of these compounds, it is clear that there are significant fluxes of ON between the atmosphere and ecosystems. It also appears that organic N can have significant effects in both spheres. The goal of our recent work in this area has been to better describe the atmospheric component of the biogeochemistry of organic nitrogen. Based on particle, gas, and fogwater samples from Northern California we have made three major findings: 1) Organic N represents a significant component, approximately 20%, of the total atmospheric N loading in these samples. This is broadly consistent with studies from other locations. 2) Amino compounds, primarily as combined amino acids, account for approximately 20% of the measured ON in our condensed phase samples. Given the properties of amino acids, these compounds could significantly affect the chemical and physical properties of atmospheric particles. 3) Organic nitrogen in atmospheric particles and drops is transformed to inorganic forms - primarily ammonium, nitrate, and nitrogen oxides (NOx) - during exposure to sunlight and/or ozone. These chemical reactions likely increase the bioavailability of the condensed phase nitrogen pool and enhance its biological effects after deposition to ecosystems.

Self assembly properties of primitive organic compounds

NASA Technical Reports Server (NTRS)

Deamer, D. W.

1991-01-01

A central event in the origin of life was the self-assembly of amphiphilic, lipid-like compounds into closed microenvironments. If a primitive macromolecular replicating system could be encapsulated within a vesicular membrane, the components of the system would share the same microenvironment, and the result would be a step toward true cellular function. The goal of our research has been to determine what amphiphilic molecules might plausibly have been available on the early Earth to participate in the formation of such boundary structures. To this end, we have investigated primitive organic mixtures present in carbonaceous meteorites such as the Murchison meteorite, which contains 1-2 percent of its mass in the form of organic carbon compounds. It is likely that such compounds contributed to the inventory of organic carbon on the prebiotic earth, and were available to participate in chemical evolution leading to the emergence of the first cellular life forms. We found that Murchison components extracted into non-polar solvent systems are surface active, a clear indication of amphiphilic character. One acidic fraction self-assembles into vesicular membranes that provide permeability barriers to polar solutes. Other evidence indicates that the membranes are bimolecular layers similar to those formed by contemporary membrane lipids. We conclude that bilayer membrane formation by primitive amphiphiles on the early Earth is feasible. However, only a minor fraction of acidic amphiphiles assembles into bilayers, and the resulting membranes require narrowly defined conditions of pH and ionic composition to be stable. It seems unlikely, therefore, that meteoritic infall was a direct source of membrane amphiphiles. Instead, the hydrocarbon components and their derivatives more probably would provide an organic stock available for chemical evolution. Our current research is directed at possible reactions which would generate substantial quantities of membranogenic amphiphiles. One possibility is photochemical oxidation of hydrocarbons.

Abiotic synthesis of organic compounds from carbon disulfide under hydrothermal conditions.

PubMed

Rushdi, Ahmed I; Simoneit, Bernd R T

2005-12-01

Abiotic formation of organic compounds under hydrothermal conditions is of interest to bio, geo-, and cosmochemists. Oceanic sulfur-rich hydrothermal systems have been proposed as settings for the abiotic synthesis of organic compounds. Carbon disulfide is a common component of magmatic and hot spring gases, and is present in marine and terrestrial hydrothermal systems. Thus, its reactivity should be considered as another carbon source in addition to carbon dioxide in reductive aqueous thermosynthesis. We have examined the formation of organic compounds in aqueous solutions of carbon disulfide and oxalic acid at 175 degrees C for 5 and 72 h. The synthesis products from carbon disulfide in acidic aqueous solutions yielded a series of organic sulfur compounds. The major compounds after 5 h of reaction included dimethyl polysulfides (54.5%), methyl perthioacetate (27.6%), dimethyl trithiocarbonate (6.8%), trithianes (2.7%), hexathiepane (1.4%), trithiolanes (0.8%), and trithiacycloheptanes (0.3%). The main compounds after 72 h of reaction consisted of trithiacycloheptanes (39.4%), pentathiepane (11.6%), tetrathiocyclooctanes (11.5%), trithiolanes (10.6%), tetrathianes (4.4%), trithianes (1.2%), dimethyl trisulfide (1.1%), and numerous minor compounds. It is concluded that the abiotic formation of aliphatic straight-chain and cyclic polysulfides is possible under hydrothermal conditions and warrants further studies.

Exploring sources of biogenic secondary organic aerosol compounds using chemical analysis and the FLEXPART model

NASA Astrophysics Data System (ADS)

Martinsson, Johan; Monteil, Guillaume; Sporre, Moa K.; Kaldal Hansen, Anne Maria; Kristensson, Adam; Eriksson Stenström, Kristina; Swietlicki, Erik; Glasius, Marianne

2017-09-01

Molecular tracers in secondary organic aerosols (SOAs) can provide information on origin of SOA, as well as regional scale processes involved in their formation. In this study 9 carboxylic acids, 11 organosulfates (OSs) and 2 nitrooxy organosulfates (NOSs) were determined in daily aerosol particle filter samples from Vavihill measurement station in southern Sweden during June and July 2012. Several of the observed compounds are photo-oxidation products from biogenic volatile organic compounds (BVOCs). Highest average mass concentrations were observed for carboxylic acids derived from fatty acids and monoterpenes (12. 3 ± 15. 6 and 13. 8 ± 11. 6 ng m-3, respectively). The FLEXPART model was used to link nine specific surface types to single measured compounds. It was found that the surface category sea and ocean was dominating the air mass exposure (56 %) but contributed to low mass concentration of observed chemical compounds. A principal component (PC) analysis identified four components, where the one with highest explanatory power (49 %) displayed clear impact of coniferous forest on measured mass concentration of a majority of the compounds. The three remaining PCs were more difficult to interpret, although azelaic, suberic, and pimelic acid were closely related to each other but not to any clear surface category. Hence, future studies should aim to deduce the biogenic sources and surface category of these compounds. This study bridges micro-level chemical speciation to air mass surface exposure at the macro level.

Molecular profiling of permafrost soil organic carbon composition and degradation

NASA Astrophysics Data System (ADS)

Gu, B.; Mann, B.

2014-12-01

Microbial degradation of soil organic matter (SOM) is a key process for terrestrial carbon (C) cycling, though the dynamics of these transformations remain unclear at the molecular level. This study reports the application of ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) to profile molecular components of Arctic SOM collected from the surface water and the mineral horizon of a low-centered polygon soil at Barrow Environmental Observatory (BEO), Barrow, Alaska. Soil samples were subjected to anaerobic warming experiments for a period of 40 days, and the SOM was extracted before and after the incubation to determine the components of organic C that were degraded over the course of the study. A CHO index based on molecular composition data was utilized to codify SOM components according to their observed degradation potential. Carbohydrate- and lignin-like compounds in the water-soluble fraction (WSF) demonstrated a high degradation potential, while structures with similar stoichiometries in the base-soluble fraction (BSF) were not readily degraded. The WSF of SOM also shifted to a wider range of measured molecular masses including an increased prevalence of larger compounds, while the size distribution of compounds in the BSF changed little over the same period. Additionally, the molecular profiling data indicated an apparently ordered incorporation of organic nitrogen in the BSF immobilized as primary and secondary amines, possibly as components of N-heterocycles, which may provide insight into nitrogen immobilization or mobilization processes in SOM. Our study represents an important step forward for studying Arctic SOM with improved understanding of the molecular properties of soil organic C and the ability to represent SOM in climate models that will predict the impact of climate change on soil C and nutrient cycling.

In-situ molecular-level elucidation of organofluorine binding sites in a whole peat soil.

PubMed

Longstaffe, James G; Courtier-Murias, Denis; Soong, Ronald; Simpson, Myrna J; Maas, Werner E; Fey, Michael; Hutchins, Howard; Krishnamurthy, Sridevi; Struppe, Jochem; Alaee, Mehran; Kumar, Rajeev; Monette, Martine; Stronks, Henry J; Simpson, André J

2012-10-02

The chemical nature of xenobiotic binding sites in soils is of vital importance to environmental biogeochemistry. Interactions between xenobiotics and the naturally occurring organic constituents of soils are strongly correlated to environmental persistence, bioaccessibility, and ecotoxicity. Nevertheless, because of the complex structural and chemical heterogeneity of soils, studies of these interactions are most commonly performed indirectly, using correlative methods, fractionation, or chemical modification. Here we identify the organic components of an unmodified peat soil where some organofluorine xenobiotic compounds interact using direct molecular-level methods. Using (19)F→(1)H cross-polarization magic angle spinning (CP-MAS) nuclear magnetic resonance (NMR) spectroscopy, the (19)F nuclei of organofluorine compounds are used to induce observable transverse magnetization in the (1)H nuclei of organic components of the soil with which they interact after sorption. The observed (19)F→(1)H CP-MAS spectra and dynamics are compared to those produced using model soil organic compounds, lignin and albumin. It is found that lignin-like components can account for the interactions observed in this soil for heptafluoronaphthol (HFNap) while protein structures can account for the interactions observed for perfluorooctanoic acid (PFOA). This study employs novel comprehensive multi-phase (CMP) NMR technology that permits the application of solution-, gel-, and solid-state NMR experiments on intact soil samples in their swollen state.

Biconnectivity of the cellular metabolism: A cross-species study and its implication for human diseases

PubMed Central

Kim, P.; Lee, D.-S.; Kahng, B.

2015-01-01

The maintenance of stability during perturbations is essential for living organisms, and cellular networks organize multiple pathways to enable elements to remain connected and communicate, even when some pathways are broken. Here, we evaluated the biconnectivity of the metabolic networks of 506 species in terms of the clustering coefficients and the largest biconnected components (LBCs), wherein a biconnected component (BC) indicates a set of nodes in which every pair is connected by more than one path. Via comparison with the rewired networks, we illustrated how biconnectivity in cellular metabolism is achieved on small and large scales. Defining the biconnectivity of individual metabolic compounds by counting the number of species in which the compound belonged to the LBC, we demonstrated that biconnectivity is significantly correlated with the evolutionary age and functional importance of a compound. The prevalence of diseases associated with each metabolic compound quantifies the compounds vulnerability, i.e., the likelihood that it will cause a metabolic disorder. Moreover, the vulnerability depends on both the biconnectivity and the lethality of the compound. This fact can be used in drug discovery and medical treatments. PMID:26490723

BIOMARKERS OF PM EXPOSURE TO COMBUSTION SOURCE EMISSIONS & ORGANIC (TOXIC) COMPONENTS

EPA Science Inventory

Fine particles (PM2.5) and associated semivolatile organic compounds (SVOC) contain a very complex mixture of both organic and inorganic chemicals that may contribute to toxicity of the particles. The health effects of PM2.5 exposures in humans result from both acute and chronic...

New Approach for Fractioning Metal Compounds Studies in Soils

NASA Astrophysics Data System (ADS)

Minkina, Tatiana; Motuzova, Galina; Mandzhieva, Saglara; Bauer, Tatiana; Burachevskaya, Marina; Sushkova, Svetlana; Nevidomskaya, Dina; Kalinitchenko, Valeriy

2016-04-01

A combined approach for fractioning metal compounds in soils on the basis of sequential (Tessier, 1979) and parallel extractions (1 N NH4Ac, pH 8; 1% EDTA in NH4Ac; and 1N HCl) is proposed. Metal compounds in sequential and parallel extracts are grouped according to the strength of their bonds with soil components. A given group includes metal compounds with similar strengths of bonds and, hence, with similar migration capacities. The groups of firmly and loosely bound metal compounds can be distinguished. This approach has been used to assess the group composition of Zn, Cu, and Pb compounds in an ordinary chernozem and its changes upon the soil contamination with metals. Contamination of an ordinary chernozem from Rostov oblast with heavy metals caused a disturbance of the natural ratios between the metal compounds. In the natural soil, firmly bound metals predominate (88-95%of the total content), which is mainly caused by the fixation of metals in lattices of silicate minerals (56-83%of the total content). The mobility of the metals in the natural soil is low (5-12%) and is mainly related to metal compounds loosely bound with the soil carbonates. Upon the soil contamination with metals (application rates of 100-300 mg/kg), the content of all the metal compounds increases, but the ratio between them shifts towards a higher portion of the potentially mobile metal compounds (up to 30-40% of the bulk contents of the metals). Organic substances and non-silicate Fe, Al, and Mn minerals become the main carriers of the firmly and loosely bound metals. The strengths of their bonds with Cu, Pb, and Zn differ. Lead in the studied chernozems is mainly fixed in a loosely bound form with organic matter, whereas copper and zinc are fixed both by the organic matter and by the non-silicate Fe, Al, and Mn compounds. Firm fixation of the applied Cu and Pb is mainly ensured by the soil organic matter and non-silicate minerals, whereas firm fixation of Zn is mainly due to non-silicate minerals. The amount of the applied metals fixed in the lattices of the silicate minerals is insignificant. Hence, all the soil components participate in the loose and firm fixation of the metals. The leading role in mobilization-immobilization of natural metal compounds in the ordinary chernozem belongs to carbonates and silicate minerals. For exogenic metal compounds, this role belongs to the soil organic matter and Fe-Mn oxides and hydroxides. The obtained data are important for ecology because they enable us to predict the transformation of soil components responsible for metal fixation and the possibility of their secondary mobilization. The danger of metal mobilization is more probable for metal compounds with organic substances that are particularly active in the loose binding of the introduced metals. This work was supported by the Ministry of Science of the Russian Federation, project no. 5.885.2014/K, the Russian Foundation for Basic Research, projects no. № 14-05-00586_a.

[Volatile organic compounds concentrations and sources inside new air-conditioned bus].

PubMed

You, Ke-Wei; Ge, Yun-Shan; Qian, Yi-Xin; Liu, Wei; Feng, Bo; Zhang, Yan-Ni; Ning, Zhan-Wu; Hu, Bin; Zhao, Shou-Tang

2008-05-01

The distributing profile and concentration level inside new air-conditioned buses with 53 seats have been determined using the method of thermal desorption-capillary GC/MS under vehicle static conditions. Compounds were identified from their mass spectral data by using US National Institute of Standards and Technology (NIST02). The total numbers of identified components were 33 inside buses, including alkenes (15,45.4%), aromatic compounds (9,27.3%), alcohols (4,12.1%), ketones (3,9.1%) and esters (2,6.1%), especially in the range of C6-C10. The top 5 compounds measured inside buses were decane (8.01 mg/m3), 3-methylhexane (7.10 mg/m3), heptane (5.10 mg/m3), isoheptane (4.20 mg/m3) and 1-Methyl-3-ethylbenzene (3.56 mg/m3), and total volatile organic compounds (TVOC) > 52.5 mg/m3. The main sources of in-vehicle hydrocarbons and aromatic compounds comes from cabin components and interior trim materials (e.g., sealants, carpets, adhesives, paints, leather, plastics, PU foam and PE foam) that may retain certain VOCs during manufacturing, and/or emit these compounds over an extended period of time from off-gassing, aging-related breakdown products, heating/cooling and so on.

Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

NASA Technical Reports Server (NTRS)

Iraci, L. T.; Michelsen, R. R.; Ashbourn, S. F. M.; Staton, S. J. R.

2003-01-01

To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

Molecular Properties of Red Wine Compounds and Cardiometabolic Benefits

PubMed Central

Markoski, Melissa M.; Garavaglia, Juliano; Oliveira, Aline; Olivaes, Jessica; Marcadenti, Aline

2016-01-01

Wine has been used since the dawn of human civilization. Despite many health benefits, there is still a lot of discussion about the real properties of its components and its actions on cells and molecular interactions. A large part of these issues permeate the fine line between the amount of alcohol that causes problems to organic systems and the amount that could be beneficial for the health. However, even after the process of fermentation, wine conserves different organic compounds from grapes, such as polysaccharides, acids, and phenolic compounds, such as flavonoids and nonflavonoids. These substances have known anti-inflammatory and antioxidant capacities, and are considered as regulatory agents in cardiometabolic process. In this study, the main chemical components present in the wine, its interaction with molecules and biological mechanisms, and their interference with intra- and extracellular signaling are reviewed. Finally, the properties of wine that may benefit cardiovascular system are also revised. PMID:27512338

Sphalerite is a geochemical catalyst for carbon−hydrogen bond activation

PubMed Central

Shipp, Jessie A.; Gould, Ian R.; Shock, Everett L.; Williams, Lynda B.; Hartnett, Hilairy E.

2014-01-01

Reactions among minerals and organic compounds in hydrothermal systems are critical components of the Earth’s deep carbon cycle, provide energy for the deep biosphere, and may have implications for the origins of life. However, there is limited information as to how specific minerals influence the reactivity of organic compounds. Here we demonstrate mineral catalysis of the most fundamental component of an organic reaction: the breaking and making of a covalent bond. In the absence of mineral, hydrothermal reaction of cis- and trans-1,2-dimethylcyclohexane is extremely slow and generates many products. In the presence of sphalerite (ZnS), however, the reaction rate increases dramatically and one major product is formed: the corresponding stereoisomer. Isotope studies show that the sphalerite acts as a highly specific heterogeneous catalyst for activation of a single carbon−hydrogen bond in the dimethylcyclohexanes. PMID:25071186

Sphalerite is a geochemical catalyst for carbon-hydrogen bond activation.

PubMed

Shipp, Jessie A; Gould, Ian R; Shock, Everett L; Williams, Lynda B; Hartnett, Hilairy E

2014-08-12

Reactions among minerals and organic compounds in hydrothermal systems are critical components of the Earth's deep carbon cycle, provide energy for the deep biosphere, and may have implications for the origins of life. However, there is limited information as to how specific minerals influence the reactivity of organic compounds. Here we demonstrate mineral catalysis of the most fundamental component of an organic reaction: the breaking and making of a covalent bond. In the absence of mineral, hydrothermal reaction of cis- and trans-1,2-dimethylcyclohexane is extremely slow and generates many products. In the presence of sphalerite (ZnS), however, the reaction rate increases dramatically and one major product is formed: the corresponding stereoisomer. Isotope studies show that the sphalerite acts as a highly specific heterogeneous catalyst for activation of a single carbon-hydrogen bond in the dimethylcyclohexanes.

SORPTION OF TOXIC ORGANIC COMPOUNDS ON WATERWATER SOLIDS: MECHANISMS AND MODELING

EPA Science Inventory

It is proposed that sorption is a combination of two fundamentally different processes: adsorption and partitioning. A sorption model was developed for both single-component and multicomponent systems. The model was tested using single-component experimental isotherm data of eig...

Source apportionment of submicron organic aerosol at an urban background and a road site in Barcelona (Spain) during SAPUSS

NASA Astrophysics Data System (ADS)

Alier, M.; van Drooge, B. L.; Dall'Osto, M.; Querol, X.; Grimalt, J. O.; Tauler, R.

2013-10-01

This study investigates the contribution of potential sources to the submicron (PM1) organic aerosol (OA) simultaneously detected at an urban background (UB) and a road site (RS) in Barcelona during the 30 days of the intensive field campaign of SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies, September-October 2010). A total of 103 filters at 12 h sampling time resolution were collected at both sites. Thirty-six neutral and polar organic compounds of known emission sources and photo-chemical transformation processes were analyzed by gas chromatography-mass spectrometry (GC-MS). The concentrations of the trace chemical compounds analyzed are herein presented and discussed. Additionally, OA source apportionment was performed by multivariate curve resolution-alternating least squares (MCR-ALS) and six OA components were identified at both sites: two were of primary anthropogenic OA origin and three of secondary OA origin, while a sixth one was not clearly defined. Primary organics from emissions of local anthropogenic activities (urban primary organic aerosol, or POA Urban), mainly traffic emissions but also cigarette smoke, contributed 43% (1.5 μg OC m-3) and 18% (0.4 μg OC m-3) to OA at RS and UB, respectively. A secondary primary source - biomass burning (BBOA) - was found in all the samples (average values 7% RS; 12% UB; 0.3 μg OC m-3), but this component was substantially contributing to OA only when the sampling sites were under influence of regional air mass circulation (REG.). Three secondary organic aerosol (SOA) components (describing overall 60% of the variance) were observed in the urban ambient PM1. Products of isoprene oxidation (SOA ISO) - i.e. 2-methylglyceric acid, C5 alkene triols and 2-methyltetrols - showed the highest abundance at both sites when the city was under influence of inland air masses. The overall concentrations of SOA ISO were similar at both sites (0.4 and 0.3 μg m-3, or 16% and 7%, at UB and RS, respectively). By contrast, a SOA biogenic component attributed to α-pinene oxidation (SOA BIO PIN) presented average concentrations of 0.5 μg m-3 at UB (24% of OA) and 0.2 μg m-3 at RS (7%), respectively, suggesting that this SOA component did not impact the two monitoring sites at the same level. A clear anti-correlation was observed between SOA ISO and SOA PIN during nucleation days, surprisingly suggesting that some of the growth of urban freshly nucleating particles may be driven by biogenic α-pinene oxidation products but inhibited by isoprene organic compounds. A third SOA component was formed by a mixture of aged anthropogenic and biogenic secondary organic compounds (SOA Aged) that accumulated under stagnant atmospheric conditions, contributing for 12% to OA at RS (0.4 μg OC m-3) and for 18% at UB (0.4 μg OC m-3). A sixth component, formed by C7-C9 dicarboxylic acids and detected especially during daytime, was called "urban oxygenated organic aerosol" (OOA Urban) due to its high abundance at urban RS (23%; 0.8 μg OCm-3) vs. UB (10%; 0.2 μg OCm-3), with a well-defined daytime maximum. This temporal trend and geographical differentiation suggests that local anthropogenic sources were determining this component. However, the changes of these organic molecules were also influenced by the air mass trajectories, indicating that atmospheric conditions have an influence on this component, although the specific origin on this component remains unclear. It points to a secondary organic component driven by primary urban sources including cooking and traffic (mainly gasoline) activities.

Source apportionment of submicron organic aerosol at an urban background and a road site in Barcelona, Spain

NASA Astrophysics Data System (ADS)

Alier, M.; van Drooge, B. L.; Dall'Osto, M.; Querol, X.; Grimalt, J. O.; Tauler, R.

2013-04-01

This study investigates the contribution of potential sources to the sub-micron (PM1) organic aerosol (OA) simultaneously detected at an urban background (UB) and a road site (RS) in Barcelona during the 30 days of the intensive field campaign of SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies, September-October 2010). 103 filters at 12 h sampling time resolution were collected at both sites. Thirty-six neutral and polar organic compounds of known emission sources and photo-chemical transformation processes were analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). The concentrations of the trace chemical compounds analyzed are herein presented and discussed. Additionally, OA source apportionment was performed by Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) and six OA components were identified at both sites: two were of primary anthropogenic OA origin, three of secondary OA origin while a sixth one was not clearly defined. Primary organics from emissions of local anthropogenic activities (Urban primary organic aerosol, Urban POA) contributed for 43% (1.5 μg OC m-3) and 18% (0.4 μg OC m-3) to OA in RS and UB, respectively. A secondary primary source - biomass burning (BBOA) - was found in all the samples (average values 7% RS; 12% UB; 0.3 μg OC m-3), but this component was substantially contributing to OA only when the sampling sites were under influence of regional air mass circulation. Three Secondary Organic Aerosol (SOA) components (describing overall 60% of the variance) were observed in the urban ambient PM1. Products of isoprene oxidation (SOA ISO), i.e. 2-methylglyceric acid, C5 alkene triols and 2-methyltetrols, showed the highest abundance at both sites when the city was under influence of inland air masses. The overall concentrations of SOA ISO were similar at both sites (0.4 and 0.3 μg m-3, 16% and 7%, at UB and RS, respectively). By contrast, a SOA biogenic component attributed to α-pinene oxidation (SOA BIO PIN) presented average concentrations of 0.5 μg m-3 at UB (24% of OA) and 0.2 μg m-3 at RS (7%), respectively, suggesting that this SOA component did not impact the two monitoring site at the same level. A clear anti correlation was observed between SOA ISO and SOA PIN during nucleation days, surprisingly suggesting that some of the growth of urban freshly nucleating particles may be driven by biogenic α-pinene oxidation products but inhibited by isoprene organic compounds. A third SOA component was formed by a mixture of aged anthropogenic and biogenic secondary organic compounds (Aged SOA) that accumulated under stagnant atmospheric conditions, contributing for 12% to OA at RS (0.4 μg OC m-3) and for 18% at UB (0.4 μg OC m-3). A sixth component, formed by C7-C9 dicarboxylic acids and detected especially during daytime, was called "urban oxygenated organic aerosol" (Urban OOA) due to its high abundance in urban RS (23%; 0.8 μg OC m-3) vs. UB (10%; 0.2 μg OC m-3), with a well-defined daytime maximum. This temporal trend and geographical differentiation suggests that local anthropogenic sources were determining this component. However, the changes of these organic molecules were also influenced by the air mass trajectories, indicating that atmospheric conditions had an influence on this component although the specific origin on this component remains unclear. It points to a secondary organic component driven by primary urban sources including cooking and traffic (mainly gasoline) activities.

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NOx conditions

NASA Astrophysics Data System (ADS)

D'Ambro, Emma L.; Lee, Ben H.; Liu, Jiumeng; Shilling, John E.; Gaston, Cassandra J.; Lopez-Hilfiker, Felipe D.; Schobesberger, Siegfried; Zaveri, Rahul A.; Mohr, Claudia; Lutz, Anna; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.; Rivera-Rios, Jean C.; Keutsch, Frank N.; Thornton, Joel A.

2017-01-01

We present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO2 and low-NO conditions, highly oxygenated (O : C ≥ 1) C5 compounds were major components (˜ 50 %) of SOA. The SOA composition and effective volatility evolved both as a function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, > 30 % of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.

Molecular and Microscopic Insights into the Formation of Soil Organic Matter in a Red Pine Rhizosphere

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

Dohnalkova, Alice C.; Tfaily, Malak M.; Smith, A. Peyton

Microbially-derived carbon inputs to soils play an important role in forming soil organic matter (SOM), but detailed knowledge of basic mechanisms of carbon (C) cycling, such as stabilization of organic C compounds originating from rhizodeposition, is scarce. This study aimed to investigate the stability of rhizosphere-produced carbon components in a model laboratory mesocosm of Pinus resinosa grown in a designed mineral soil mix with limited nutrients. We utilized a suite of advanced imaging and molecular techniques to obtain a molecular-level identification of newly-formed SOM compounds, and considered implications regarding their degree of long-term persistence. The microbes in this controlled, nutrient-limitedmore » system, without pre-existing organic matter, produced extracellular polymeric substances that formed associations with nutrient-bearing minerals and contributed to the microbial mineral weathering process. Electron microscopy revealed unique ultrastructural residual signatures of biogenic C compounds, and the increased presence of an amorphous organic phase associated with the mineral phase was evidenced by X-ray diffraction. Here, these findings provide insight into the formation of SOM products in ecosystems, and show that the plant- and microbially-derived material associated with mineral matrices may be important components in current soil carbon models.« less

Molecular and Microscopic Insights into the Formation of Soil Organic Matter in a Red Pine Rhizosphere

DOE PAGES

Dohnalkova, Alice C.; Tfaily, Malak M.; Smith, A. Peyton; ...

2017-08-26

Microbially-derived carbon inputs to soils play an important role in forming soil organic matter (SOM), but detailed knowledge of basic mechanisms of carbon (C) cycling, such as stabilization of organic C compounds originating from rhizodeposition, is scarce. This study aimed to investigate the stability of rhizosphere-produced carbon components in a model laboratory mesocosm of Pinus resinosa grown in a designed mineral soil mix with limited nutrients. We utilized a suite of advanced imaging and molecular techniques to obtain a molecular-level identification of newly-formed SOM compounds, and considered implications regarding their degree of long-term persistence. The microbes in this controlled, nutrient-limitedmore » system, without pre-existing organic matter, produced extracellular polymeric substances that formed associations with nutrient-bearing minerals and contributed to the microbial mineral weathering process. Electron microscopy revealed unique ultrastructural residual signatures of biogenic C compounds, and the increased presence of an amorphous organic phase associated with the mineral phase was evidenced by X-ray diffraction. Here, these findings provide insight into the formation of SOM products in ecosystems, and show that the plant- and microbially-derived material associated with mineral matrices may be important components in current soil carbon models.« less

Urey onboard Exomars: Searching for life

NASA Astrophysics Data System (ADS)

Ehrenfreund, Pascale

Exomars is the flagship mission of the European exploration program Aurora. The main goal of the Exomars mission is to further characterize the environment on Mars and to search for life. Data from recent Mars missions indicate the presence of liquid water for a geologically relevant period of time. If life arose during that period, evidence in the form of organic compounds might still be present on Mars today. A fundamental challenge ahead for the Exomars mission is to search for extinct and extant life using a sophisticated drill and innovative life detection instruments. Urey: Mars Organic and Oxidant Detector has been selected for the Pasteur payload and is considered a key instrument to achieve the mission's scientific objectives. Urey will target several key classes of organic molecules such as amino acids, nucleobases, aminosugars as well as polycyclic aromatic hydrocrabon (PAHs) using state-of-the-art analytical methods. The sensitivity of Urey to detect organic compounds in the Martian regolith is unprecedented (part-per-trillions). Efficient extraction of organic molecules using a sub-critical water extractor and subsequent concentration through sublimation renders a sample that is best suited to be analyzed by the sensitive mµCE system. The capability of the mµCE component to distinguish chiral amino acids will give direct evidence for abiotic or biotic compound origin. Another Urey component, the Mars Oxidation Instument, will deploy chemoresistor oxidant sensors to take complementary measurements evaluating the survival potential of organic compounds in the environment. We report on the progress of instrument development and related field tests in the Atacama desert.

Relationship between organic precursors and N-nitrosodimethylamine (NDMA) formation in tropical water sources.

PubMed

Qi, Wang; Fang Yee, Lim; Jiangyong, Hu

2014-12-01

The presence of organic compounds in water sources is one of the concerns in water treatment. They are potential precursors of disinfection byproducts (DBPs) and thus induce health problems in humans. Among the emerging DBPs, carcinogenic compound N-nitrosodimethylamine (NDMA) has been receiving attention during the last decade. This study examined the characteristics of organic components in various water sources and investigated their relationships with NDMA formation. Experiments were carried out on selected water samples from both natural water and wastewater. Results showed similar NDMA formation kinetics for both water sources. However, more contribution of NDMA precursors was found to be from the wastewater due to its higher organic nitrogen content. NDMA formation potential (NDMAFP) of secondary effluent ranged from 264 to 530 ng/L. A correlation study between organic compound characteristics and NDMAFP indicated that the majority of NDMA precursors came from dissolved organic nitrogen (DON) compound with small molecular weight (smaller than 500 Da), with correlation R(2) = 0.898. Although secondary treatment removed more than 90% of NDMA precursors, the remaining precursors in secondary effluent would still pose a challenge for water quality.

Confined-Pyrolysis as an Experimental Method for Hydrothermal Organic Synthesis

NASA Technical Reports Server (NTRS)

Leif, Roald N.; Simoneit, Bernd R. T.

1995-01-01

A closed pyrolysis system has been developed as a tool for studying the reactions of organic compounds under extreme hydrothermal conditions. Small high pressure stainless steel vessels in which the ratio of sediment or sample to water has been adjusted to eliminate the headspace at peak experimental conditions confines the organic components to the bulk solid matrix and eliminates the partitioning of the organic compounds away from the inorganic components during the experiment. Confined pyrolysis experiments were performed to simulate thermally driven catagenetic changes in sedimentary organic matter using a solids to water ratio of 3.4 to 1. The extent of alteration was measured by monitoring the steroid and triterpenoid biomarkers and polycyclic aromatic hydrocarbon distributions. These pyrolysis experiments duplicated the hydrothermal transformations observed in nature. Molecular probe experiments using alkadienes, alkenes and alkanes in H2O and D2O elucidated the isomerization and hydrogenation reactions of aliphatic and the competing oxidative reactions occurring under hydrothermal conditions. This confined pyrolysis technique is being applied to test experiments on organic synthesis of relevance to chemical evolution for the origin of life.

40 CFR 59.102 - Standards.

Code of Federal Regulations, 2010 CFR

2010-07-01

... VOLATILE ORGANIC COMPOUND EMISSION STANDARDS FOR CONSUMER AND COMMERCIAL PRODUCTS National Volatile Organic... § 59.106 of this subpart, any coating resulting from the mixing instructions of a regulated entity must... § 59.104(a). (b) Different combinations or mixing ratios of coating components constitute different...

Fluorescence spectroscopy as a specific tool for the interaction study of two surfactants with natural and synthetic organic compounds

NASA Astrophysics Data System (ADS)

Jung, Aude-Valérie; Frochot, Céline; Bersillon, Jean-Luc

2016-04-01

Four different techniques were used to study the binding of cationic cetyltrimethylammonium bromide (CTAB) and non-ionic nonylphenylethoxyl (NPE) surfactants to three synthetic organic components that mimic humic-like aggregates and to two natural aggregated humic substances (HS) extracted from aquatic suspended matter. The composition of synthetic organic components were chosen to be similar to high molecular weight highly processed terrigenous HS and low and high molecular weight less processed terrigenous (or aquatic terrigenous) HS. The natural HS were extracted under two different meteorological conditions (rainy and dry periods). No significant interaction between the non-ionic surfactant and any of the studied compounds was found. Concerning CTAB; pH, conductivity and turbidity measurements, along with fluorescence spectroscopy were combined to provide a better understanding of interactions between organic aggregates and the surfactant. The spectroscopic data show that a "highly processed terrigenous HS" fluorophore interacts in a different way with the cationic surfactant than an "aquatic terrigenous (or less processed terrigenous) HS" fluorophore does. Under similar conditions, some spectral changes in the fluorescence signal are correlated to changes in non-specific physical-chemical parameters (pH, turbidity, conductivity) for the organic compounds tested. The complexation mechanism is essentially governed by charge neutralization, which can be monitored specifically by the fluorescence of the organic moieties.

Gas Separation Using Organic-Vapor-Resistent Membranes In Conjunctin With Organic-Vapor-Selective Membranes

DOEpatents

Baker, Richard W.; Pinnau, Ingo; He, Zhenjie; Da Costa, Andre R.; Daniels, Ramin; Amo, Karl D.; Wijmans, Johannes G.

2003-06-03

A process for treating a gas mixture containing at least an organic compound gas or vapor and a second gas, such as natural gas, refinery off-gas or air. The process uses two sequential membrane separation steps, one using membrane selective for the organic compound over the second gas, the other selective for the second gas over the organic vapor. The second-gas-selective membranes use a selective layer made from a polymer having repeating units of a fluorinated polymer, and demonstrate good resistance to plasticization by the organic components in the gas mixture under treatment, and good recovery after exposure to liquid aromatic hydrocarbons. The membrane steps can be combined in either order.

Source Term Modeling for Evaluating the Potential Impacts to Groundwater of Fluids Escaping from a Depleted Oil Reservoir Used for Carbon Sequestration

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

Cantrell, Kirk J.; Brown, Christopher F.

2014-06-13

In recent years depleted oil reservoirs have received special interest as carbon storage reservoirs because of their potential to offset costs through collaboration with enhanced oil recovery projects. Modeling is currently being conducted to evaluate potential risks to groundwater associated with leakage of fluids from depleted oil reservoirs used for storage of CO2. Modeling results reported here focused on understanding how toxic organic compounds found in oil will distribute between the various phases within a storage reservoir after introduction of CO2, understanding the migration potential of these compounds, and assessing potential groundwater impacts should leakage occur. Two model scenarios weremore » conducted to evaluate how organic components in oil will distribute among the phases of interest (oil, CO2, and brine). The first case consisted of 50 wt.% oil and 50 wt.% water; the second case was 90 wt.% CO2 and 10 wt.% oil. Several key organic compounds were selected for special attention in this study based upon their occurrence in oil at significant concentrations, relative toxicity, or because they can serve as surrogate compounds for other more highly toxic compounds for which required input data are not available. The organic contaminants of interest (COI) selected for this study were benzene, toluene, naphthalene, phenanthrene, and anthracene. Partitioning of organic compounds between crude oil and supercritical CO2 was modeled using the Peng-Robinson equation of state over temperature and pressure conditions that represent the entire subsurface system (from those relevant to deep geologic carbon storage environments to near surface conditions). Results indicate that for a typical set of oil reservoir conditions (75°C, and 21,520 kPa) negligible amounts of the COI dissolve into the aqueous phase. When CO2 is introduced into the reservoir such that the final composition of the reservoir is 90 wt.% CO2 and 10 wt.% oil, a significant fraction of the oil dissolves into the vapor phase. As the vapor phase moves up through the stratigraphic column, pressures and temperatures decrease, resulting in significant condensation of oil components. The heaviest organic components condense early in this process (at higher pressures and temperatures), while the lighter components tend to remain in the vapor phase until much lower pressures and temperatures are reached. Based on the model assumptions, the final concentrations of COI to reach an aquifer at 1,520 kPa and 25°C were quite significant for benzene and toluene, whereas the concentrations of polynuclear aromatic hydrocarbons that reach the aquifer were very small. This work demonstrates a methodology that can provide COI source term concentrations in CO2 leaking from a reservoir and entering an overlying aquifer for use in risk assessments.« less

Dissolving and melting phenomena of inorganic and organic crystals by addition of third or second components

NASA Astrophysics Data System (ADS)

Funakoshi, Kunio; Negishi, Rina; Nakagawa, Hiroshi; Kawasaki, Rentaro

2017-06-01

Dissolution of potassium sulphate (K2SO4) crystals was decelerated or stopped since the trivalent chrome ions (Cr(III)) or the iron ions were added into a K2SO4 aqueous solution, but inhibition mechanism of crystal dissolving by additives is not discussed well. Moreover, the melting inhibition of organic compound crystals by addition of the second components is not reported. In this study, inorganic or organic compound crystals are dissolved in a solution added the third component or were melted in a melt added the second one, and the dissolving and melting inhibition phenomena of the inorganic and organic crystals with additives are discussed. The dissolving rates of K2SO4 crystals decreased with the increasing of the amount of Cr(III) added into an K2SO4 unsaturated solution. The melting rates of m-chloronitrobenzene (CNB) crystals were also decreased by addition of p-CNB. The dissolving rates of a K2SO4 mother crystal and the melting rates of a m-CNB mother crystal were scattered during experiments and the dissolving and the melting phenomena would be caused by adsorption and detachments of additives on and from crystal surfaces.

78 FR 31921 - Agency Information Collection Activities; Submission to OMB for Review and Approval; Comment...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-05-28

... Requirements for National Volatile Organic Compound Emission Standards for Automobile Refinish Coatings, EPA... potentially affected by this action as respondents are manufacturers and importers of automobile refinish coatings and coating components. Manufacturers of automobile refinish coatings and coating components fall...

Sugar-Related Organic Compounds in Carbonaceous Meteorites

NASA Technical Reports Server (NTRS)

Cooper, G.; Kimmich, N.; Belisle, W.; Sarinana, J.; Brabham, K.; Garrel, L.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

Sugars and related polyols are critical components of all organisms and may have been necessary for the origin of life. To date, this class of organic compounds had not been definitively identified in meteorites. This study was undertaken to determine if polyols were present in the early Solar System as constituents of carbonaceous meteorites. Results of analyses of the Murchison and Murray meteorites indicate that formaldehyde and sugar chemistry may be responsible for the presence of a variety of polyols. We conclude that polyols were present on the early Earth through delivery by asteroids and possibly comets.

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.

Irradiated Benzene Ice Provides Clues to Meteoritic Organic Chemistry

NASA Technical Reports Server (NTRS)

Callahan, Michael Patrick; Gerakines, Perry Alexander; Martin, Mildred G.; Hudson, Reggie L.; Peeters, Zan

2013-01-01

Aromatic hydrocarbons account for a significant portion of the organic matter in carbonaceous chondrite meteorites, as a component of both the low molecular weight, solvent-extractable compounds and the insoluble organic macromolecular material. Previous work has suggested that the aromatic compounds in carbonaceous chondrites may have originated in the radiation-processed icy mantles of interstellar dust grains. Here we report new studies of the organic residue made from benzene irradiated at 19 K by 0.8 MeV protons. Polyphenyls with up to four rings were unambiguously identified in the residue by gas chromatography-mass spectrometry. Atmospheric pressure photoionization Fourier transform mass spectrometry was used to determine molecular composition, and accurate mass measurements suggested the presence of polyphenyls, partially hydrogenated polyphenyls, and other complex aromatic compounds. The profile of low molecular weight compounds in the residue compared well with extracts from the Murchison and Orgueil meteorites. These results are consistent with the possibility that solid phase radiation chemistry of benzene produced some of the complex aromatics found in meteorites.

Carbonaceous meteorites as a source of sugar-related organic compounds for the early Earth

NASA Technical Reports Server (NTRS)

Cooper, G.; Kimmich, N.; Belisle, W.; Sarinana, J.; Brabham, K.; Garrel, L.

2001-01-01

The much-studied Murchison meteorite is generally used as the standard reference for organic compounds in extraterrestrial material. Amino acids and other organic compounds important in contemporary biochemistry are thought to have been delivered to the early Earth by asteroids and comets, where they may have played a role in the origin of life. Polyhydroxylated compounds (polyols) such as sugars, sugar alcohols and sugar acids are vital to all known lifeforms-they are components of nucleic acids (RNA, DNA), cell membranes and also act as energy sources. But there has hitherto been no conclusive evidence for the existence of polyols in meteorites, leaving a gap in our understanding of the origins of biologically important organic compounds on Earth. Here we report that a variety of polyols are present in, and indigenous to, the Murchison and Murray meteorites in amounts comparable to amino acids. Analyses of water extracts indicate that extraterrestrial processes including photolysis and formaldehyde chemistry could account for the observed compounds. We conclude from this that polyols were present on the early Earth and therefore at least available for incorporation into the first forms of life.

Study of the organic matter in the DSDP /JOIDES/ cores, legs 10-15. [Deep Sea Drilling Program

NASA Technical Reports Server (NTRS)

Simoneit, B. R. T.; Burlingame, A. L.

1974-01-01

The composition of the organic matter collected on legs 10 to 15 of the DSDP (Deep Sea Drilling Project) is described. Distributions of various alkanes, carboxylic acids, steroids and terpenoids, isoprenoid ketones and olefins, and aromatic polycyclic compounds are given. Samples analyzed had terrigenous clay components, with variable organic carbon contents and thus diverse solvent soluble matter. The distribution patterns for the various compound series monitored were of marine derivation, with the terrigenous components superimposed. Diagenesis of steroids appeared to proceed via both stanones and stanols to their respective steranes. Degradative processes were observed to be operative: oxidative products, mainly ketones derived from steroids and phytol, were identified, probably due to microbial alteration prior to or during sedimentation. Loss of alkane and fatty acid C preferences and presence of polycyclic aromatics evinced maturation. Results indicate that the accumulation, degradation, diagenesis and maturation of organic matter occurs in various steps in the deep sea environment.

Analysis of Volatile Organic Compounds Emitted by Plant Growth-Promoting Fungus Phoma sp. GS8-3 for Growth Promotion Effects on Tobacco

PubMed Central

Naznin, Hushna Ara; Kimura, Minako; Miyazawa, Mitsuo; Hyakumachi, Mitsuro

2013-01-01

We extracted volatile organic compounds (VOCs) emitted by a plant growth-promoting fungus (PGPF) Phoma sp. GS8-3 by gas chromatography and identified them by mass spectrometry. All of the identified compounds belonged to C4-C8 hydrocarbons. Volatiles varied in number and quantity by the culture period of the fungus (in days). 2-Methyl-propanol and 3-methyl-butanol formed the main components of the volatile blends for all the culture periods of fungus. Growth-promoting effects of the identified synthetic compounds were analyzed individually and in blends using tobacco plants. We found that the mixture of volatiles extracted from 3-day-old culture showed significant growth promotion in tobacco in vitro. The volatile blend showed better growth promotion at lower than higher concentrations. Our results confirm the potential role of volatile organic compounds in the mechanism of growth enhancement by GS8-3. PMID:23080408

Catalysts for the hydrodenitrogenation of organic materials and process for the preparation of the catalysts

DOEpatents

Laine, R.M.; Hirschon, A.S.; Wilson, R.B. Jr.

1987-12-29

A process is described for the preparation of a multimetallic catalyst for the hydrodenitrogenation of an organic feedstock, which process comprises: (a) forming a precatalyst itself comprising: (1) a first metal compound selected from compounds of nickel, cobalt or mixtures thereof; (2) a second metal compound selected from compounds of chromium, molybdenum, tungsten, or mixtures thereof; and (3) an inorganic support; (b) heating the precatalyst of step (a) with a source of sulfide in a first non-oxidizing gas at a temperature and for a time effective to presulfide the precatalyst; (c) adding in a second non-oxidizing gas to the sulfided precatalyst of step (b) an organometallic transition metal moiety selected from compounds of iridium, rhodium, iron, ruthenium, tungsten or mixtures thereof for a time and at a temperature effective to chemically combine the metal components; and (d) optionally heating the chemically combined catalyst of step (b) in vacuum at a temperature and for a time effective to remove residual volatile organic materials. 12 figs.

Review of the Toxicity of the Metallic Compounds Proposed for Use in the New Green Missile Formulation

NASA Technical Reports Server (NTRS)

Major, Michael A.

2000-01-01

In an effort to modernize and minimize hazards posed by the toxic components of missile propellant, the USACHPPM has been tasked to provide a comparison of the toxicity of compounds currently in use as missile propellants and the suite of compounds proposed to replace them. This report deals with the portion of this work concerning the toxicity of the organometallic compounds used in these formulations. Toxicity assessments of the organic compounds used in these formulations are published elsewhere. In general, toxicity data were available for all the metal compounds of concern or for closely related compounds that can serve as surrogates for the assessment of toxicity. We have high confidence in the reliability of these comparisons. This report is organized by element to provide the reader with an in-depth assessment with a minimum of redundancy. The narrative will first describe general concepts about the toxicity of each metal and then provide a summary of the toxicological information available for the specific compound.

Evidence from the Pacific troposphere for large global sources of oxygenated organic compounds

NASA Astrophysics Data System (ADS)

Singh, H.; Chen, Y.; Staudt, A.; Jacob, D.; Blake, D.; Heikes, B.; Snow, J.

2001-04-01

The presence of oxygenated organic compounds in the troposphere strongly influences key atmospheric processes. Such oxygenated species are, for example, carriers of reactive nitrogen and are easily photolysed, producing free radicals-and so influence the oxidizing capacity and the ozone-forming potential of the atmosphere-and may also contribute significantly to the organic component of aerosols. But knowledge of the distribution and sources of oxygenated organic compounds, especially in the Southern Hemisphere, is limited. Here we characterize the tropospheric composition of oxygenated organic species, using data from a recent airborne survey conducted over the tropical Pacific Ocean (30°N to 30°S). Measurements of a dozen oxygenated chemicals (carbonyls, alcohols, organic nitrates, organic pernitrates and peroxides), along with several C2-C8 hydrocarbons, reveal that abundances of oxygenated species are extremely high, and collectively, oxygenated species are nearly five times more abundant than non-methane hydrocarbons in the Southern Hemisphere. Current atmospheric models are unable to correctly simulate these findings, suggesting that large, diffuse, and hitherto-unknown sources of oxygenated organic compounds must therefore exist. Although the origin of these sources is still unclear, we suggest that oxygenated species could be formed via the oxidation of hydrocarbons in the atmosphere, the photochemical degradation of organic matter in the oceans, and direct emissions from terrestrial vegetation.

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NO x conditions

DOE PAGES

D'Ambro, Emma L.; Lee, Ben H.; Liu, Jiumeng; ...

2017-01-04

Here, we present measurements of secondary organic aerosol (SOA) formation from isoprene photochemical oxidation in an environmental simulation chamber at a variety of oxidant conditions and using dry neutral seed particles to suppress acid-catalyzed multiphase chemistry. A high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) utilizing iodide-adduct ionization coupled to the Filter Inlet for Gases and Aerosols (FIGAERO) allowed for simultaneous online sampling of the gas and particle composition. Under high-HO 2 and low-NO conditions, highly oxygenated (O : C ≥ 1) C 5 compounds were major components (~50%) of SOA. The SOA composition and effective volatility evolved both as amore » function of time and as a function of input NO concentrations. Organic nitrates increased in both the gas and particle phases as input NO increased, but the dominant non-nitrate particle-phase components monotonically decreased. We use comparisons of measured and predicted gas-particle partitioning of individual components to assess the validity of literature-based group-contribution methods for estimating saturation vapor concentrations. While there is evidence for equilibrium partitioning being achieved on the chamber residence timescale (5.2 h) for some individual components, significant errors in group-contribution methods are revealed. In addition, >30% of the SOA mass, detected as low-molecular-weight semivolatile compounds, cannot be reconciled with equilibrium partitioning. These compounds desorb from the FIGAERO at unexpectedly high temperatures given their molecular composition, which is indicative of thermal decomposition of effectively lower-volatility components such as larger molecular weight oligomers.« less

ORGANIC AEROSOL SAMPLING AND ANALYSIS METHODS RESEARCH

EPA Science Inventory

Carbonaceous material is a major component of ambient PM at all locations in the U.S. and it is composed of two major classes: organic carbon (OC, composed of hundreds of individual compounds) and elemental carbon (EC, also referred to as soot, black carbon, or light adsorbing ca...

40 CFR 469.12 - Specialized definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... AND STANDARDS ELECTRICAL AND ELECTRONIC COMPONENTS POINT SOURCE CATEGORY Semiconductor Subcategory... in 40 CFR part 136 apply to this subpart. In addition, (a) The term “total toxic organics (TTO)” means the sum of the concentrations for each of the following toxic organic compounds which is found in...

40 CFR 469.12 - Specialized definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... AND STANDARDS ELECTRICAL AND ELECTRONIC COMPONENTS POINT SOURCE CATEGORY Semiconductor Subcategory... in 40 CFR part 136 apply to this subpart. In addition, (a) The term “total toxic organics (TTO)” means the sum of the concentrations for each of the following toxic organic compounds which is found in...

Natural deep eutectic solvents as the major mobile phase components in high-performance liquid chromatography-searching for alternatives to organic solvents.

PubMed

Sutton, Adam T; Fraige, Karina; Leme, Gabriel Mazzi; da Silva Bolzani, Vanderlan; Hilder, Emily F; Cavalheiro, Alberto J; Arrua, R Dario; Funari, Cristiano Soleo

2018-06-01

Over the past six decades, acetonitrile (ACN) has been the most employed organic modifier in reversed-phase high-performance liquid chromatography (RP-HPLC), followed by methanol (MeOH). However, from the growing environmental awareness that leads to the emergence of "green analytical chemistry," new research has emerged that includes finding replacements to problematic ACN because of its low sustainability. Deep eutectic solvents (DES) can be produced from an almost infinite possible combinations of compounds, while being a "greener" alternative to organic solvents in HPLC, especially those prepared from natural compounds called natural DES (NADES). In this work, the use of three NADES as the main organic component in RP-HPLC, rather than simply an additive, was explored and compared to the common organic solvents ACN and MeOH but additionally to the greener ethanol for separating two different mixtures of compounds, one demonstrating the elution of compounds with increasing hydrophobicity and the other comparing molecules of different functionality and molar mass. To utilize NADES as an organic modifier and overcome their high viscosity monolithic columns, temperatures at 50 °C and 5% ethanol in the mobile phase were used. NADES are shown to give chromatographic performances in between those observed for ACN and MeOH when eluotropic strength, resolution, and peak capacity were taken into consideration, while being less environmentally impactful as shown by the HPLC-Environmental Assessment Tool (HPLC-EAT) metric. With the development of proper technologies, DES could open a new class of mobile phases increasing the possibilities of new separation selectivities while reducing the environmental impact of HPLC analyses. Graphical abstract Natural deep eutectic solvents versus traditional solvents in HPLC.

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.;

Electrosorption of organic acids from aqueous bio-oil and conversion into hydrogen via microbial electrolysis cells

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

Park, Lydia Kyoung-Eun; Satinover, Scott J.; Yiacoumi, Sotira

Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted watermore » and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H 2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutral process.« less

Electrosorption of organic acids from aqueous bio-oil and conversion into hydrogen via microbial electrolysis cells

DOE PAGES

Park, Lydia Kyoung-Eun; Satinover, Scott J.; Yiacoumi, Sotira; ...

2018-02-17

Neutralization of the bio-oil pH has been shown to generate a neutralized bio-oil aqueous phase (NBOAP) that includes most of the acidic components and a neutralized bio-oil organic phase (NBOOP) that includes hydrophobic organics, such as phenols. NBOOP can be used for fuel production, while NBOAP can be fed to microbial electrolysis cells (MECs) for hydrogen production. After pH neutralization, some organic acidic components remain in NBOOP. This work is focused on capturing acidic compounds from NBOOP through water extraction and electrosorption, and demonstrating hydrogen production via MECs. Capacitive deionization (CDI) is proven effective in capturing ions from NBOOP-contacted watermore » and NBOAP via electrosorption. Captured acidic compounds enable the MEC application to effectively produce renewable hydrogen. Chemical oxygen demand (COD) removal of 49.2%, 61.5%, and 60.8% for 2, 4, and 10 g/L-anode/day loading were observed, corresponding to a total COD degradation of 0.19 g/L, 0.79 g/L, and 1.3 g/L, respectively. A maximum hydrogen productivity of 4.3 L-H 2/L-anode/day was obtained. Major compounds in the water phase such as fatty acids, sugar derivatives, furanic and phenolic compounds were converted to hydrogen with an efficiency of 80–90%. Lastly, this approach may lead the entire biomass pyrolysis process to be an overall carbon-neutral process.« less

Hydrophobization potential of organic compounds deriving from olive oil production waste water

NASA Astrophysics Data System (ADS)

Egerer, Sina E.; Bandow, Nicole; Marschner, Bernd; Schaumann, Gabriele E.

2010-05-01

Olive oil production waste water (OPWW) is rich in dissolved organic carbon and nutrients (e.g. potassium). In order to use it as organic fertilizer, small-scale and family run olive oil production farms in Israel and Palestine often discharge it directly onto agricultural land without any previous treatment. One unwanted side effect that can be observed is the development of soil water repellency (SWR) which is probably induced by amphiphilic substances. Previous studies on the composition of OPWW have shown that it contains oil components such as phenols, fats and large-molecular organic compounds (e.g. Gonzalezvila et al., 1995), some of which have been reported to induce water repellency on soil mineral surfaces (e.g. Ma'shum et al., 1988; Leelamanie and Karube, 2007). For prioritization of compounds the individual hydrophobization potential of 16 common OPWW components was systematically evaluated using the sessile drop and the Wilhelmy plate method. Acid-washed sand was taken as model soil mineral material. In a batch experiment OPWW samples from Israel and Palestine were applied to sand and two different soils in order to investigate their hydrophobization potential under different temperature and humidity conditions. To facilitate the identification of the chemicals responsible for inducing SWR, a fractionation procedure was applied to fraction the OPWW samples using solvents of different polarity. The prioritized compounds were analyzed by GC-MS. First results of this identification will be presented as well.

Hygroscopicity and volatility of semi-volatile organic components in optical levitated single organic/inorganic aqueous aerosol droplet

NASA Astrophysics Data System (ADS)

Cai, C.; Zhao, C.

2017-12-01

Quantifying the gas/particle partitioning of organic compounds is of great significance to the understanding of atmospheric aerosol indirect effect. Accurate determination of the hygroscopicities and vapor pressures of semi-volatile organic compounds (SVOC) is of crucial importance in studying their partitioning behavior into atmospheric aerosol, as current published vapor pressures results of compounds of interest (usually with vapor pressures smaller than 0.01 Pa) vary by several orders of magnitude. On the other hand, influences on SVOCs evaporation from participation of inorganic species remains ambiguous. In this study we present quantitative investigation of hygroscopicities and volatilities of single aerosol droplets in an aerosol optical tweezers. The trapped droplet (3-7 µm radii) in the aerosol optical tweezers acts as a micro cavity, which stimulates the cavity enhanced Raman spectroscopy (CERS) signal. Size and composition of the particle are calculated from Mie fit to the positions of the "whispering gallery modes" in the CERS fingerprint. Hygroscopic behaviors and SVOC pure component vapor pressure can then be extracted from the correlation between the changing droplet radius and solute concentration (derived from experimentally determined RI real part). We will further present the influences between mass transfer on the gas-particle interface and within the droplet.

Comparison of the chemical composition of dissolved organic matter in three lakes in Minnesota

USGS Publications Warehouse

Cao, Xiaoyan; Aiken, George R.; Butler, Kenna D.; Mao, Jingdong; Schmidt-Rohr, Klaus

2018-01-01

New information on the chemical composition of dissolved organic matter (DOM) in three lakes in Minnesota has been gained from spectral editing and two-dimensional nuclear magnetic resonance (NMR) methods, indicating the effects of lake hydrological settings on DOM composition. Williams Lake (WL), Shingobee Lake (SL), and Manganika Lake (ML) had different source inputs, and the lake water residence time (WRT) of WL was markedly longer than that of SL and ML. The hydrophobic organic acid (HPOA) and transphilic organic acid (TPIA) fractions combined comprised >50% of total DOM in these lakes, and contained carboxyl-rich alicyclic molecules (CRAM), aromatics, carbohydrates, and N-containing compounds. The previously understudied TPIA fractions contained fewer aromatics, more oxygen-rich CRAM, and more N-containing compounds compared to the corresponding HPOA. CRAM represented the predominant component in DOM from all lakes studied, and more so in WL than in SL and ML. Aromatics including lignin residues and phenols decreased in relative abundances from ML to SL and WL. Carbohydrates and N-containing compounds were minor components in both HPOA and TPIA and did not show large variations among the three lakes. The increased relative abundances of CRAM in DOM from ML, SL to WL suggested the selective preservation of CRAM with increased residence time.

The chemistry and beneficial bioactivities of carvacrol (4-isopropyl-2-methylphenol), a component of essential oils produced by aromatic plants and spices

USDA-ARS?s Scientific Manuscript database

Aromatic plants produce organic compounds that may be involved in the defense of plants against phytopathogenic insects, bacteria, fungi, and viruses. One of these compounds called carvacrol that is found in high concentrations in essential oils such as oregano has been reported to exhibit numerous...

Formation of high-molecular-weight compounds via the heterogeneous reactions of gaseous C8-C10 n-aldehydes in the presence of atmospheric aerosol components

NASA Astrophysics Data System (ADS)

Han, Yuemei; Kawamura, Kimitaka; Chen, Qingcai; Mochida, Michihiro

2016-02-01

A laboratory study on the heterogeneous reactions of straight-chain aldehydes was performed by exposing n-octanal, nonanal, and decanal vapors to ambient aerosol particles. The aerosol and blank filters were extracted using methanol. The extracts were nebulized and the resulting compositions were examined using a high-resolution time-of-flight aerosol mass spectrometer. The mass spectral analysis showed that the exposures of the aldehydes to aerosol samples increased the peak intensities in the high mass range. The peaks in the mass spectra of the aerosol samples after exposure to different aldehydes were characterized by a homologous series of peak shifts due to the addition of multiple CH2 units. This result is explained by the formation of high-molecular-weight (HMW) compounds that contain single or multiple aldehyde moieties. The HMW fragment peaks for the blank filters exposed to n-aldehydes were relatively weak, indicating an important contribution from the ambient aerosol components to the formation of the HMW compounds. Among the factors affecting the overall interaction of aldehydes with atmospheric aerosol components, gas phase diffusion possibly limited the reactions under the studied conditions; therefore, their occurrence to a similar degree in the atmosphere is not ruled out, at least for the reactions involving n-nonanal and decanal. The major formation pathways for the observed HMW products may be the self-reactions of n-aldehydes mediated by atmospheric aerosol components and the reactions of n-aldehydes with organic aerosol components. The observed formation of HMW compounds encourages further investigations into their effects on the aerosol properties as well as the organic aerosol mass in the atmosphere.

The Effect of Fermentation Broth Components on Performance of High Silica ZSM-5/Silicone Rubber Mixed Matrix Membranes

EPA Science Inventory

Fermentative organisms produce a range of compounds in addition to the desired product. For example, in addition to ethanol, standard yeast produces longer straight-chained and branched alcohols and organic acids. Additionally, biomass pretreatment process, particularly acid-base...

Organic compound composition in soil and sediments collected in Jackson, Mississippi.

PubMed

Gołębiowski, Marek; Stepnowski, Piotr; Hemmingway, Tometrick; Leszczyńska, Danuta

2016-01-01

The aim of our study was to identify organic pollutants found in soil and sediment samples collected within the Jackson, MS metropolitan area. The chemical characterization of the organic compound fractions in soil and sediment samples was carried out by separating the organic fraction using column chromatography (CC) and quantitatively analyzing the polycyclic aromatic hydrocarbons (PAHs), n-alkanes and other organic compounds using gas chromatography-electron impact mass spectrometry (GC-MS). Fifty-six compounds were identified and quantified in the soil samples and 33 compounds were identified and quantified in the sediment samples. The PAHs, n-alkanes and other organic compound profiles in the soil and sediment samples were compared. The percentage contents of the organic compounds in the soil samples were very diverse (from traces to 12.44 ± 1.47%). The compounds present in the highest concentrations were n-alkanes: n-C31 (12.44 ± 1.47%), n-C29 (11.64 ± 1.21%), and n-C33 (8.95 ± 1.08%). The components occurring in smaller quantities (from 1% to 5%) were 2 PAHs (fluoranthene 1.28 ± 0.25%, pyrene 1.16 ± 0.20%), 10 n-alkanes from n-C21 (1.25 ± 0.29%) to n-C32 (2.67 ± 0.52%) and 11 other compounds (e.g., 2-pentanol, 4-methyl (3.33 ± 0.44%), benzyl butyl phthalate (4.25 ± 0.59%), benzenedicarboxylic acid (1.14 ± 0.08%), ethane, 1,1-diethoxy (3.15 ± 0.41) and hexadecanoic acid (2.52 ± 0.34). The soil samples also contained 30 compounds present in concentrations <1% (e.g., anthracene (0.13 ± 0.04%), n-C20 (0.84 ± 0.21%) and acetic acid (0.12 ± 0.04%). The compounds present in the highest concentrations in the sediment samples were PAHs: pyrene (7.73 ± 1.15%) and fluoranthene (6.23 ± 1.07%) and n-alkanes: n-C31 (6.74 ± 1.21%), n-C29 (6.65 ± 0.98%) and n-C27 (6.13 ± 1.09%). The remaining organic compounds were present in smaller quantities (< 5%).

Enabling the identification, quantification, and characterization of organics in complex mixtures to understand atmospheric aerosols

NASA Astrophysics Data System (ADS)

Isaacman, Gabriel Avram

Particles in the atmosphere are known to have negative health effects and important but highly uncertain impacts on global and regional climate. A majority of this particulate matter is formed through atmospheric oxidation of naturally and anthropogenically emitted gases to yield highly oxygenated secondary organic aerosol (SOA), an amalgamation of thousands of individual chemical compounds. However, comprehensive analysis of SOA composition has been stymied by its complexity and lack of available measurement techniques. In this work, novel instrumentation, analysis methods, and conceptual frameworks are introduced for chemically characterizing atmospherically relevant mixtures and ambient aerosols, providing a fundamentally new level of detailed knowledge on their structures, chemical properties, and identification of their components. This chemical information is used to gain insights into the formation, transformation and oxidation of organic aerosols. Biogenic and anthropogenic mixtures are observed in this work to yield incredible complexity upon oxidation, producing over 100 separable compounds from a single precursor. As a first step toward unraveling this complexity, a method was developed for measuring the polarity and volatility of individual compounds in a complex mixture using two-dimensional gas chromatography, which is demonstrated in Chapter 2 for describing the oxidation of SOA formed from a biogenic compound (longifolene: C15H24). Several major products and tens of substantial minor products were produced, but none could be identified by traditional methods or have ever been isolated and studied in the laboratory. A major realization of this work was that soft ionization mass spectrometry could be used to identify the molecular mass and formula of these unidentified compounds, a major step toward a comprehensive description of complex mixtures. This was achieved by coupling gas chromatography to high resolution time-of-flight mass spectrometry with vacuum ultraviolet (VUV) photo-ionization. Chapters 3 and 4 describe this new analytical technique and its initial application to determine the structures of unknown compounds and formerly unresolvable mixtures, including a complete description of the chemical composition of two common petroleum products related to anthropogenic emissions: diesel fuel and motor oil. The distribution of hydrocarbon isomers in these mixtures - found to be mostly of branched, cyclic, and saturated -- is described with unprecedented detail. Instead of measuring average bulk aerosol properties, the methods developed and applied in this work directly measure the polarity, volatility, and structure of individual components to allow a mechanistic understanding of oxidation processes. Novel characterizations of these complex mixtures are used to elucidate the role of structure and functionality in particle-phase oxidation, including in Chapter 4 the first measurements of relative reaction rates in a complex hydrocarbon particle. Molecular structure is observed to influence particle-phase oxidation in unexpected and important ways, with cyclization decreasing reaction rates by ~30% and branching increasing reaction rates by ~20-50%. The observed structural dependence is proposed to result in compositional changes in anthropogenic organic aerosol downwind of urban areas, which has been confirmed in subsequent work by applying the techniques described here. Measurement of organic aerosol components is extended to ambient environments through the development of instrumentation with the unprecedented capability to measure hourly concentrations and gas/particle partitioning of individual highly oxygenated organic compounds in the atmosphere. Chapters 5 and 6 describe development of new procedures and hardware for the calibration and analysis of oxygenates using the Semi-Volatile Thermal desorption Aerosol Gas chromatograph (SV-TAG), a custom instrument for in situ quantification of gas- and particle-phase organic compounds in the atmosphere. High time resolution measurement of oxygenated compounds is achieved through a reproducible and quantitative methodology for in situ "derivatization" -- replacing highly polar functional groups that cannot be analyzed by traditional gas chromatography with less polar groups. Implementation of a two-channel sampling system for the simultaneous collection of particle-phase and total gas-plus-particle phase samples allows for the first direct measurements of gas/particle partitioning in the atmosphere, significantly advancing the study of atmospheric composition and variability, as well as the processes governing condensation and re-volatilization. This work presents the first in situ measurements of a large suite of highly oxygenated biogenic oxidation products in both the gas- and particle-phase. Isoprene, the most ubiquitous biogenic emission, oxidizes to form 2-methyltetrols and C5 alkene triols, while α-pinene, the most common monoterpene, forms pinic, pinonic, hydroxyglutaric, and other acids. These compounds are reported in Chapter 7 with unprecedented time resolution and are shown for the first time to have a large gas-phase component, contrary to typical assumptions. Hourly comparisons of these products with anthropogenic aerosol components elucidate the interaction of human and natural emissions at two rural sites: the southeastern, U.S. and Amazonia, Brazil. Anthropogenic influence on SOA formation is proposed to occur through the increase in liquid water caused by anthropogenic sulfate. Furthermore, these unparalleled observations of gas/particle partitioning of biogenic oxidation products demonstrate that partitioning of oxygenates is unexpectedly independent of volatility: many volatile, highly oxygenated compounds have a large particle-phase component that is poorly described by traditional models. These novel conclusions are reached in part by applying the new frameworks developed in previous chapters to understand the properties of unidentified compounds, demonstrating the importance of detailed characterization of atmospheric organic mixtures. Comprehensive analysis of anthropogenic and biogenic emissions and oxidation product mixtures is coupled in this work with high time-resolution measurement of individual organic components to yield significant insights into the transformations of organic aerosols. Oxidation chemistry is observed in both laboratory and field settings to depend on molecular properties, volatility, and atmospheric composition. However, this work demonstrates that these complex processes can be understood through the quantification of individual known and unidentified compounds, combined with their classification into descriptive frameworks.

Volatile organic chemicals of a shore-dwelling cyanobacterial mat community.

PubMed

Evans, W G

1994-02-01

The main components of a cyanobacterial mat community of a hypersaline lake shore consist of edaphic, mat-forming strains (ecophenes), and littoral strains ofOscillatoria animalis Agardh andO. subbrevis Schmidle, other microorganisms associated with these cyanobacteria, several species ofBembidion (Carabidae: Coleoptera), and two halophytic flowering plants:Puccinellia nuttalliana (salt meadow grass) andSalicornia europaea rubra (samphire). The volatile organic compounds of this community are a blend of those emitted by each of these components such as the C17 alka(e)nes, geosmin, 2-methylisoborneol,β-cyclocitral,β-ionone, dimethyl sulfide, and dimethyl trisulfide of cyanobacteria and associated microorganisms; alcohols, esters, and aldehydes usually associated with flowering plants; and possibly some insect-derived esters, particularly isopropyl tetradecanoate. The dominant compounds were: C11, C13, C15, and C17 alka(e)nes, methyl esters of C16 and C18:2 acids, isopropyl tetradecanoate, heptanal, 3-octanone and 2-nonanone, the acyclic terpene linalool, and the alcohols 1-heptanol, 1-hexanol, 1-octanol, 3-hexen-1-ol, and 2-octen-1-ol. It is concluded that this community may be distinguished from related communities by its repertoire of volatile organic compounds.

Characterization of organic material in ice core samples from North America, Greenland, and Antarctica using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry

NASA Astrophysics Data System (ADS)

Catanzano, V.; Grannas, A. M.; Sleighter, R. L.; Hatcher, P. G.

2013-12-01

Historically, it has been an analytical challenge to detect and identify the organic components present in ice cores, due to the low abundance of organic carbon. In order to detect and characterize the small amounts of organic matter in ice cores, ultra high resolution instrumentation is required. Here we report the use of ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry, coupled with electrospray ionization, to identify the molecular formulas and compound classes of organic matter in both modern and ancient ice core and glacial samples from Wyoming, Greenland, and Antarctica. A suite of 21 samples were analyzed and thousands of distinct molecular species were identified in each sample, providing clues to the nature and sources of organic matter in these regions. Major biochemical classes of compounds were detected such as lignins, tannins, carbohydrates, proteins, lipids, unsaturated hydrocarbons, and condensed aromatic compounds. We will compare the nature of the organic matter present in the samples in order to determine the differences in dominant organic compound classes and in heteroatom (nitrogen and sulfur) abundance. By analyzing these differences, it is possible to investigate the historical patterns of organic matter deposition/source, and begin to investigate the influence of climate change, volcanism, and onset of the industrial revolution on the nature of organic matter preserved in ice cores.

Detecting and Eliminating Interfering Organic Compounds in Waters Analyzed for Isotopic Composition by Crds

NASA Astrophysics Data System (ADS)

Richman, B. A.; Hsiao, G. S.; Rella, C.

2010-12-01

Optical spectroscopy based CRDS technology for isotopic analysis of δD and δ18O directly from liquid water has greatly increased the number and type of liquid samples analyzed. This increase has also revealed a previously unrecognized sample contamination problem. Recently West[1] and Brand[2] identified samples containing ethanol, methanol, plant extracts and other organic compounds analyzed by CRDS and other spectroscopy based techniques as yielding erroneous results for δD and δ18O (especially δD) due to spectroscopic interference. Not all organic compounds generate interference. Thus, identifying which samples are contaminated by which organic compounds is of key importance for data credibility and correction. To address this problem a new approach in the form of a software suite, ChemCorrect™, has been developed. A chemometrics component uses a spectral library of water isotopologues and interfering organic compounds to best fit the measured spectra. The best fit values provide a quantitative assay of the actual concentrations of the various species and are then evaluated to generate a visual flag indicating samples affected by organic contamination. Laboratory testing of samples spiked with known quantities of interfering organic compounds such as methanol, ethanol, and terpenes was performed. The software correctly flagged and identified type of contamination for all the spiked samples without any false positives. Furthermore the reported values were a linear function of actual concentration with an R^2>0.99 even for samples which contained multiple organic compounds. Further testing was carried out against a range of industrial chemical compounds which can contaminate ground water as well as a variety of plant derived waters and juices which were also analyzed by IRMS. The excellent results obtained give good insight into which organic compounds cause interference and which classes of plants are likely to contain interfering compounds. Finally approaches to minimize the effect of interfering compounds will be discussed including methods to assess the confidence level of an isotopic value obtained from a contaminated sample. [1] Rapid Commun. Mass Spectrom. 2010; 24: 1-7 [2] Rapid Commun. Mass Spectrom. 2009; 23: 1879-1884 Results from laboratory samples, most of which were spiked with interfering organic compounds. Samples are color coded as follows: blue=standard, green=no contamination, yellow=slight contamination, red=heavily contaminated.

Myeloperoxidase-hydrogen peroxide-chloride antimicrobial system: effect of exogenous amines on antibacterial action against Escherichia coli.

PubMed

Thomas, E L

1979-07-01

Exogenous ammonium ions (NH(4) (+)) and amine compounds had a profound influence on the antibacterial activity of the myeloperoxidase-hydrogen peroxide-chloride system against Escherichia coli. The rate of killing increased in the presence of NH(4) (+) and certain guanidino compounds and decreased in the presence of alpha-amino acids, polylysine, taurine, or tris (hydroxymethyl) aminomethane. Myeloperoxidase catalyzed the oxidation of chloride to hypochlorous acid, which reacted either with bacterial amine or amide components or both or with the exogenous compounds to yield chloramine or chloramide derivatives or both. These nitrogen-chlorine derivatives could oxidize bacterial components. Killing was correlated with oxidation of bacterial components. The rate of oxidation of bacterial sulfhydryls increased in the presence of the compounds that increased the rate of killing and decreased in the presence of the other compounds. The reaction of HOCl with NH(4) (+) yielded monochloramine (NH(2)Cl), which could be extracted into organic solvents. The N-Cl derivatives of bacterial components or of polylysine, taurine, or tris(hydroxymethyl)aminomethane could not be extracted. The effect of NH(4) (+) on killing is attributed to the ability of NH(2)Cl to penetrate the hydrophobic cell membrane and thus to oxidize intracellular components. Polylysine, taurine, and tris(hydroxymethyl)aminomethane formed high-molecular-weight, charged, or polar N-Cl derivatives that would be unable to penetrate the cell membrane. These results suggest an important role for leukocyte amine components in myeloperoxidase-catalyzed antimicrobial activity in vivo.

Instrument for Analysis of Organic Compounds on Other Planets

NASA Technical Reports Server (NTRS)

Daulton, Riley M.; Hintze, Paul E.

2016-01-01

The goal of this project is to develop the Instrument for Solvent Extraction and Analysis of Extraterrestrial Bodies using In Situ Resources (ISEE). Specifically, ISEE will extract and characterize organic compounds from regolith which is found on the surface of other planets or asteroids. The techniques this instrument will use are supercritical fluid extraction (SFE) and supercritical fluid chromatography (SFC). ISEE aligns with NASA's goal to expand the frontiers of knowledge, capability, and opportunities in space in addition to supporting NASA's aim to search for life elsewhere by characterizing organic compounds. The outcome of this project will be conceptual designs of 2 components of the ISEE instrument as well as the completion of proof-of-concept extraction experiments to demonstrate the capabilities of SFE. The first conceptual design is a pressure vessel to be used for the extraction of the organic compounds from the regolith. This includes a comparison of different materials, geometry's, and a proposition of how to insert the regolith into the vessel. The second conceptual design identifies commercially available fluid pumps based on the requirements needed to generate supercritical CO2. The proof-of-concept extraction results show the percent mass lost during standard solvent extractions of regolith with organic compounds. This data will be compared to SFE results to demonstrate the capabilities of ISEE's approach.

40 CFR 59.103 - Container labeling requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... National Volatile Organic Compound Emission Standards for Automobile Refinish Coatings § 59.103 Container... automobile refinish coating or coating component container or package, the day, month, and year on which the...

40 CFR 59.103 - Container labeling requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... National Volatile Organic Compound Emission Standards for Automobile Refinish Coatings § 59.103 Container... automobile refinish coating or coating component container or package, the day, month, and year on which the...

40 CFR 59.103 - Container labeling requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... National Volatile Organic Compound Emission Standards for Automobile Refinish Coatings § 59.103 Container... automobile refinish coating or coating component container or package, the day, month, and year on which the...

Environmental Aspects of Two Volatile Organic Compound Groundwater Treatment Designs at the Rocky Flats Site - 13135

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

Michalski, Casey C.; DiSalvo, Rick; Boylan, John

2013-07-01

DOE's Rocky Flats Site in Colorado is a former nuclear weapons production facility that began operations in the early 1950's. Because of releases of hazardous substances to the environment, the federally owned property and adjacent offsite areas were placed on the CERCLA National Priorities List in 1989. The final remedy was selected in 2006. Engineered components of the remedy include four groundwater treatment systems that were installed before closure as CERCLA-accelerated actions. Two of the systems, the Mound Site Plume Treatment System and the East Trenches Plume Treatment System, remove low levels of volatile organic compounds using zero-valent iron media,more » thereby reducing the loading of volatile organic compounds in surface water resulting from the groundwater pathway. However, the zero-valent iron treatment does not reliably reduce all volatile organic compounds to consistently meet water quality goals. While adding additional zero-valent iron media capacity could improve volatile organic compound removal capability, installation of a solar powered air-stripper has proven an effective treatment optimization in further reducing volatile organic compound concentrations. A comparison of the air stripper to the alternative of adding additional zero-valent iron capacity to improve Mound Site Plume Treatment System and East Trenches Plume Treatment System treatment based on several key sustainable remediation aspects indicates the air stripper is also more 'environmentally friendly'. These key aspects include air pollutant emissions, water quality, waste management, transportation, and costs. (authors)« less

A new multidimensional stoichiometric classification of compounds: moving beyond the van Krevelen diagram.

NASA Astrophysics Data System (ADS)

Rivas-Ubach, A.; Liu, Y.; Bianchi, T. S.; Tolic, N.; Jansson, C.; Paša-Tolić, L.

2017-12-01

The role of nutrients in organisms, especially primary producers, has been a topic of special interest in ecosystem research for understanding the ecosystem structure and function. The majority of macro-elements in organisms, such as C, H, O, N and P, do not act as single elements but are components of organic compounds (lipids, peptides, carbohydrates, etc), which are more directly related to the physiology of organisms and thus to the ecosystem function. However, accurately deciphering the overall content of the main compound classes (lipids, proteins, carbohydrates,…) in organisms is still a major challenge. van Krevelen (vK) diagrams have been widely used as an estimation of the main compound categories present in environmental samples based on O:C vs H:C molecular ratios, but a stoichiometric classification based exclusively on O:C and H:C ratios is feeble. Different compound classes show large O:C and H:C ratio overlapping and other heteroatoms, such as N and P, should be considered to robustly distinguish the different classes. We propose a new compound classification for biological/environmental samples based on the C:H:O:N:P stoichiometric ratios of thousands of molecular formulas of characterized compounds from 6 different main categories: lipids, peptides, amino-sugars, carbohydrates, nucleotides and phytochemical compounds (oxy-aromatic compounds). This new multidimensional stoichiometric compound constraints classification (MSCC) can be applied to data obtained with high resolution mass spectrometry (HRMS), allowing an accurate overview of the relative abundances of the main compound categories present in organismal samples. The MSCC has been optimized for plants, but it could be also applied to different organisms and serve as a strong starting point to further investigate other environmental complex matrices (soils, aerosols, etc). The proposed MSCC advances environmental research, especially eco-metabolomics, ecophysiology and ecological stoichiometry studies, providing a new tool to understand the ecosystem structure and function at the molecular level.

Selective gas-chromatographic detection using an ion-selective electrode-II Selective detection of fluorine compounds.

PubMed

Kojima, T; Ichise, M; Seo, Y

1972-04-01

Components in samples are separated on a gas chromatography column using hydrogen as carrier gas. The individual components from the column are passed through a platinum tube heated at 1000 degrees , where they undergo hydrogenolysis, and fluorine compounds are converted into hydrogen fluoride. The hydrogen fluoride is dissolved in a slow stream of an absorption solution, and the fluoride ion concentration in the resulting solution is monitored in a flow-cell with a fluoride ion electrode. The potentiometric output of the cell is converted into a signal, which is proportional to the concentration of fluoride ion, by an antilogarithmic converter, and recorded. The response of the detector to fluorine compounds was about 10,000 times that to an equal quantity of other organic compounds, and 5 x 10(-11) mole of fluorobenzene could be detected.

In-depth molecular characterization and biodegradability of water-extractable organic nitrogen in Erhai Lake sediment.

PubMed

Zhang, Li; Wang, Shengrui; Yang, Jiachun; Xu, Kechen

2018-05-08

Dissolved organic nitrogen (DON) constitutes a significant fraction of the total dissolved nitrogen content of most aquatic systems and is thus a major nitrogen source for bacteria and phytoplankton. The present work applied Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to a compound-level analysis of the depth-dependent molecular composition of water-extractable organic nitrogen (WEON) in lake sediment. The study focused on Erhai Lake, China. It was found that a large portion (from 16.33 ± 7.87 to 39.54 ± 5.77%) of the WEON in the lake sediment was reactive under cultivation by algal or bacteria. The WEON in the mid-region of Erhai sediment particularly exhibited a lower bioavailability, having been less affected by the basin environment. The FT-ICR MS results revealed the presence of thousands of compounds in the Erhai Lake sediment samples collected at different depths, with the N-containing compounds accounting for 28.3-34.4% of all the compounds. The WEON molecular weight was also observed to increase with increasing sediment depth. A van Krevelen diagram showed that the lignin-type components were dominant (~ 56.2%) in the sediment WEON, contributing to its stabilization and reducing the risk of sediment nutrient release. The FT-ICR MS results further revealed 204 overlapping formulas of WEON for each core sediment sample, attributable to the presence of refractory components. It was observed that 78.4% of the formulas were within the lignin-like region, suggesting unique allochthonous DON sources. The aliphatic component proportion of all the unique formulas was also found to increase with increasing sediment depth. This indicates that, with the development and evolution of the Erhai Basin, the more labile WEON components were transformed into more stable lignin-like substrates, with a positive effect on the Lake Erhai ecosystem. Graphical abstract ᅟ.

Volatile organic compounds and particulates as components of diesel engine exhaust gas

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

Schulz, H.; Bandeira de Melo, G.; Ousmanov, F.

1999-07-01

Volatile organic compounds (VOC) and soot particles have been determined in a Diesel`s exhaust gas. A new sampling method allowed the measurement of emissions of organic compounds (C{sub 1} to C{sub 20}) in a gas chromatogram at a detection limit of ca. 0.2 mg/m{sup 3}. Particles were collected with a filter bed of ceramic particles and characterized by temperature programmed desorption (TPD) and oxidation (TPO). Engine runs were always performed at a fixed and constant air to fuel equivalence ratio ({lambda}) and with a constant volumetric efficiency, because these parameters strongly influenced the emissions in terms of both composition andmore » order of magnitude. The effective combustion temperature again strongly governed the nature of the emissions. Model fuels, composed of individual paraffins and aromatics and additions of sulfur compounds and an organic nitrate (for cetane number enhancement) were used. The results contribute to the understanding of the origin of specific emissions from Diesel engines. These newly developed methods are recommended for further application.« less

Laboratory Detection and Analysis of Organic Compounds in Rocks Using HPLC and XRD Methods

NASA Technical Reports Server (NTRS)

Dragoi, D.; Kanik, I.; Bar-Cohen, Y.; Sherrit, S.; Tsapin, A.; Kulleck, J.

2004-01-01

In this work we describe an analytical method for determining the presence of organic compounds in rocks, limestone, and other composite materials. Our preliminary laboratory experiments on different rocks/limestone show that the organic component in mineralogical matrices is a minor phase on order of hundreds of ppm and can be better detected using high precision liquid chromatography (HPLC). The matrix, which is the major phase, plays an important role in embedding and protecting the organic molecules from the harsh Martian environment. Some rocks bear significant amounts of amino acids therefore, it is possible to identify these phases using powder x-ray diffraction (XRD) by crystallizing the organic. The method of detection/analysis of organics, in particular amino acids, that have been associated with life will be shown in the next section.

Exploring astrobiology using in silico molecular structure generation.

PubMed

Meringer, Markus; Cleaves, H James

2017-12-28

The origin of life is typically understood as a transition from inanimate or disorganized matter to self-organized, 'animate' matter. This transition probably took place largely in the context of organic compounds, and most approaches, to date, have focused on using the organic chemical composition of modern organisms as the main guide for understanding this process. However, it has gradually come to be appreciated that biochemistry, as we know it, occupies a minute volume of the possible organic 'chemical space'. As the majority of abiotic syntheses appear to make a large set of compounds not found in biochemistry, as well as an incomplete subset of those that are, it is possible that life began with a significantly different set of components. Chemical graph-based structure generation methods allow for exhaustive in silico enumeration of different compound types and different types of 'chemical spaces' beyond those used by biochemistry, which can be explored to help understand the types of compounds biology uses, as well as to understand the nature of abiotic synthesis, and potentially design novel types of living systems.This article is part of the themed issue 'Reconceptualizing the origins of life'. © 2017 The Authors.

Exploring astrobiology using in silico molecular structure generation

NASA Astrophysics Data System (ADS)

Meringer, Markus; Cleaves, H. James

2017-11-01

The origin of life is typically understood as a transition from inanimate or disorganized matter to self-organized, `animate' matter. This transition probably took place largely in the context of organic compounds, and most approaches, to date, have focused on using the organic chemical composition of modern organisms as the main guide for understanding this process. However, it has gradually come to be appreciated that biochemistry, as we know it, occupies a minute volume of the possible organic `chemical space'. As the majority of abiotic syntheses appear to make a large set of compounds not found in biochemistry, as well as an incomplete subset of those that are, it is possible that life began with a significantly different set of components. Chemical graph-based structure generation methods allow for exhaustive in silico enumeration of different compound types and different types of `chemical spaces' beyond those used by biochemistry, which can be explored to help understand the types of compounds biology uses, as well as to understand the nature of abiotic synthesis, and potentially design novel types of living systems. This article is part of the themed issue 'Reconceptualizing the origins of life'.

A microfluidic device for open loop stripping of volatile organic compounds.

PubMed

Cvetković, Benjamin Z; Dittrich, Petra S

2013-03-01

The detection of volatile organic compounds is of great importance for assessing the quality of water. In this contribution, we describe a miniaturized stripping device that allows fast online detection of organic solvents in water. The core component is a glass microfluidic chip that facilitates the creation of an annular-flowing stream of water and nitrogen gas. Volatile compounds are transferred efficiently from the water into the gas phase along the microfluidic pathway at room temperature within less than 5 s. Before exiting the microchip, the liquid phase is separated from the enriched gas phase by incorporating side capillaries through which the hydrophilic water phase is withdrawn. The gas phase is conveniently collected at the outlet reservoir by tubing. Finally, a semiconductor gas sensor analyzes the concentration of (volatile) organic compounds in the nitrogen gas. The operation and use of the stripping device is demonstrated for the organic solvents THF, 1-propanol, toluene, ethylbenzene, benzaldehyde, and methanol. The mobile, inexpensive, and continuously operating system with liquid flow rates in the low range of microliters per minute can be connected to other detectors or implemented in chemical production line for process control.

A chemometrics as a powerful tool in the elucidation of the role of metals in the biosynthesis of volatile organic compounds in Hungarian thyme samples.

PubMed

Arsenijević, Jelena; Marković, Jelena; Soštarić, Ivan; Ražić, Slavica

2013-10-01

The volatile fraction of the leaves of Thymus pannonicus All. (Lamiaceae) was analyzed by headspace extraction followed by GC-FID and GC-MS analysis. The different headspace profiles were recognized, with citral and with monoterpene hydrocarbons as dominant compounds. In addition, the determination of Cr, Co, Ni, Mo, Cu, Zn, Mn, Fe, Mg, Ca, K and Na was conducted by spectroscopic techniques (FAAS, GFAAS and ICP-OES). In order to evaluate the relationship between volatile organic compounds and metals, a chemometrics approach was applied. The data obtained by analysis of the headspace and elemental content were subjected to correlation analysis, factor analysis, principal component analysis and cluster analysis. A number of significant correlations of metals with plant volatiles were found. Correlation of Zn with citral, Mn with oxygenated monoterpenes and Mg with β-bourbonene, could be explained by involvement of metals in the biosynthesis of volatile organic compounds. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

Method for acid oxidation of radioactive, hazardous, and mixed organic waste materials

DOEpatents

Pierce, Robert A.; Smith, James R.; Ramsey, William G.; Cicero-Herman, Connie A.; Bickford, Dennis F.

1999-01-01

The present invention is directed to a process for reducing the volume of low level radioactive and mixed waste to enable the waste to be more economically stored in a suitable repository, and for placing the waste into a form suitable for permanent disposal. The invention involves a process for preparing radioactive, hazardous, or mixed waste for storage by contacting the waste starting material containing at least one organic carbon-containing compound and at least one radioactive or hazardous waste component with nitric acid and phosphoric acid simultaneously at a contacting temperature in the range of about 140.degree. C. to about 210 .degree. C. for a period of time sufficient to oxidize at least a portion of the organic carbon-containing compound to gaseous products, thereby producing a residual concentrated waste product containing substantially all of said radioactive or inorganic hazardous waste component; and immobilizing the residual concentrated waste product in a solid phosphate-based ceramic or glass form.

Evaluation of PEMFC System Contaminants on the Performance of Pt Catalyst via Cyclic Voltammetry: Preprint

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

Wang, H.; Macomber, C.; Dinh, H. N.

2012-07-01

Using electrochemical cyclic voltammetry as a quick ex-situ screening tool, the impact of the extracted solution and the individual leachable constituents from prospective BOP component materials on the performance and recoverability of the platinum catalyst were evaluated. Taking an extract from Zytel{trademark} HTN51G35HSLR (PPA) as an example, the major leachable organic components are caprolactam and 1,6 hexanediol. While these organic compounds by themselves do poison the Pt catalyst to some extent, such influence is mostly recoverable by means of potential holding and potential cycling. The extracted solution, however, shows a more drastic poisoning effect and it was not recoverable. Thereforemore » the non-recoverable poisoning effect observed for the extracted solution is not from the two organic species studied. This demonstrates the complexity of such a contaminant study. Inorganic compounds that are known poisons like sulfur even in very low concentrations, may have a more dominant effect on the Pt catalyst and the recoverability.« less

A Model Study to Unravel the Complexity of Bio-Oil from Organic Wastes.

PubMed

Croce, Annamaria; Battistel, Ezio; Chiaberge, Stefano; Spera, Silvia; De Angelis, Francesco; Reale, Samantha

2017-01-10

Binary and ternary mixtures of cellulose, bovine serum albumin (BSA) and tripalmitin, as biomass reference compounds for carbohydrates, proteins and triglycerides, respectively, were treated under hydrothermal liquefaction (HTL) conditions to describe the main reaction pathways involved in the process of bio-oil production from municipal organic wastes. Several analytical techniques (elemental analysis, GC-MS, atmospheric-pressure photo-ionisation high-resolution Fourier transform ion cyclotron resonance mass spectrometry, and 13 C cross-polarisation magic-angle spinning NMR spectroscopy) were used for the molecular-level characterisation of the resulting aqueous phase, solid residue and bio-oil, in particular. The main reaction pathways led to free fatty acids, fatty acid amides, 2,5-diketopiperazines and Maillard-type compounds as the main components of the bio-oil. The relationship of such compounds to the original components of the biomass was thus determined, which highlights the fate of the heteroatom-containing molecules in particular. Finally, the molecular composition of the bio-oils from our reference compounds was matched with that of the bio-oil from municipal organic waste biomass by comparing their high-resolution Fourier transform ion cyclotron resonance mass spectra, and we obtained a surprisingly high similarity. Hence, the ternary mixture acts as a reliable biomass model and is a powerful tool to clarify the degradation mechanisms that occur in the biomass under HTL treatment, with the ultimate goal to improve the HTL process itself by modulating the input of the organic starting matter and then the upgrading steps to bio-fuels. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular Isotopic Characterization of the ALH 85013.50 Meteorite: Defining the Extraterrestrial Organic Compounds

NASA Technical Reports Server (NTRS)

Fuller, M.; Huang, Y.

2003-01-01

The Antarctic Meteorite Program has returned over 16,000 meteorites from the ice sheets of the Antarctic. This more than doubles the number of preexisting meteorite collection and adds important and rare specimens to the assemblage. The CM carbonaceous chondrites are of particular interest because of their high organic component. The Antarctic carbonaceous chondrites provide a large, previously uninvestigated suite of meteorites. Of the 161 CM chondrites listed in the Catalogue of Meteorites 138 of them have been recovered from the Antarctic ice sheets,. However, these meteorites have typically been exposed to Earth s conditions for long periods of time. The extent of terrestrial organic contamination and weathering that has taken place on these carbonaceous chondrites is unknown. In the past, stable isotope analysis was used to identify bulk organics that were extraterrestrial in origin. Although useful, this method could not exclude the possibility of terrestrial contamination contributing to the isotopic measurement. Compound specific isotope analysis of organic meteorite material has provided the opportunity to discern the terrestrial contamination from extraterrestrial organic compounds on the molecular level.

Determination of vapor pressures for nonpolar and semipolar organic compounds from gas chromatographic retention data

USGS Publications Warehouse

Hinckley, D.A.; Bidleman, T.F.; Foreman, W.T.; Tuschall, J.R.

1990-01-01

Vapor pressures for nonpolar and moderately polar organochlorine, pyrethroid, and organophosphate insecticides, phthalate esters, and organophosphate flame retardants were determined by capillary gas chromatography (GC). Organochlorines and polycyclic aromatic hydrocarbons with known liquid-phase vapor pressures (P??L) (standard compounds) were chromatographed along with two reference compounds n-C20 (elcosane) and p,p???-DDT on a 1.0-m-long poly(dimethylsiloxane) bonded-phase (BP-1) column to determine their vapor pressures by GC (P??GC). A plot of log P??L vs log P??GC for standard compounds was made to establish a correlation between measured and literature values, and this correlation was then used to compute P??L of test compounds from their measured P??GC. P??L of seven major components of technical chlordane, endosulfan and its metabolites, ??-hexachlorocyclohexane, mirex, and two components of technical toxaphene were determined by GC. This method provides vapor pressures within a factor of 2 of average literature values for nonpolar compounds, similar to reported interlaboratory precisions of vapor pressure determinations. GC tends to overestimate vapor pressures of moderately polar compounds. ?? 1990 American Chemical Society.

Automated Solid Phase Extraction (SPE) LC/NMR Applied to the Structural Analysis of Extractable Compounds from a Pharmaceutical Packaging Material of Construction.

PubMed

Norwood, Daniel L; Mullis, James O; Davis, Mark; Pennino, Scott; Egert, Thomas; Gonnella, Nina C

2013-01-01

The structural analysis (i.e., identification) of organic chemical entities leached into drug product formulations has traditionally been accomplished with techniques involving the combination of chromatography with mass spectrometry. These include gas chromatography/mass spectrometry (GC/MS) for volatile and semi-volatile compounds, and various forms of liquid chromatography/mass spectrometry (LC/MS or HPLC/MS) for semi-volatile and relatively non-volatile compounds. GC/MS and LC/MS techniques are complementary for structural analysis of leachables and potentially leachable organic compounds produced via laboratory extraction of pharmaceutical container closure/delivery system components and corresponding materials of construction. Both hyphenated analytical techniques possess the separating capability, compound specific detection attributes, and sensitivity required to effectively analyze complex mixtures of trace level organic compounds. However, hyphenated techniques based on mass spectrometry are limited by the inability to determine complete bond connectivity, the inability to distinguish between many types of structural isomers, and the inability to unambiguously determine aromatic substitution patterns. Nuclear magnetic resonance spectroscopy (NMR) does not have these limitations; hence it can serve as a complement to mass spectrometry. However, NMR technology is inherently insensitive and its ability to interface with chromatography has been historically challenging. This article describes the application of NMR coupled with liquid chromatography and automated solid phase extraction (SPE-LC/NMR) to the structural analysis of extractable organic compounds from a pharmaceutical packaging material of construction. The SPE-LC/NMR technology combined with micro-cryoprobe technology afforded the sensitivity and sample mass required for full structure elucidation. Optimization of the SPE-LC/NMR analytical method was achieved using a series of model compounds representing the chemical diversity of extractables. This study demonstrates the complementary nature of SPE-LC/NMR with LC/MS for this particular pharmaceutical application. The identification of impurities leached into drugs from the components and materials associated with pharmaceutical containers, packaging components, and materials has historically been done using laboratory techniques based on the combination of chromatography with mass spectrometry. Such analytical techniques are widely recognized as having the selectivity and sensitivity required to separate the complex mixtures of impurities often encountered in such identification studies, including both the identification of leachable impurities as well as potential leachable impurities produced by laboratory extraction of packaging components and materials. However, while mass spectrometry-based analytical techniques have limitations for this application, newer analytical techniques based on the combination of chromatography with nuclear magnetic resonance spectroscopy provide an added dimension of structural definition. This article describes the development, optimization, and application of an analytical technique based on the combination of chromatography and nuclear magnetic resonance spectroscopy to the identification of potential leachable impurities from a pharmaceutical packaging material. The complementary nature of the analytical techniques for this particular pharmaceutical application is demonstrated.

Estimating Grass-Soil Bioconcentration of Munitions Compounds from Molecular Structure.

PubMed

Torralba Sanchez, Tifany L; Liang, Yuzhen; Di Toro, Dominic M

2017-10-03

A partitioning-based model is presented to estimate the bioconcentration of five munitions compounds and two munition-like compounds in grasses. The model uses polyparameter linear free energy relationships (pp-LFERs) to estimate the partition coefficients between soil organic carbon and interstitial water and between interstitial water and the plant cuticle, a lipid-like plant component. Inputs for the pp-LFERs are a set of numerical descriptors computed from molecular structure only that characterize the molecular properties that determine the interaction with soil organic carbon, interstitial water, and plant cuticle. The model is validated by predicting concentrations measured in the whole plant during independent uptake experiments with a root-mean-square error (log predicted plant concentration-log observed plant concentration) of 0.429. This highlights the dominant role of partitioning between the exposure medium and the plant cuticle in the bioconcentration of these compounds. The pp-LFERs can be used to assess the environmental risk of munitions compounds and munition-like compounds using only their molecular structure as input.

Characterization of organic matter in cloud waters sampled at the puy de Dôme mountain using FT-ICR-MS

NASA Astrophysics Data System (ADS)

Bianco, A.; Chaumerliac, N.; Vaitilingom, M.; Deguillaume, L.; Bridoux, M. C.

2017-12-01

The chemical composition of organic matter in cloud water is highly complex. The organic species result from their dissolution from the gas phase or from the soluble fraction of the particle phase. They are also produced by aqueous phase reactivity. Several low molecular weight organic species have been quantified such as aldehydes and carboxylic acids. Recently, amino acids were also detected in cloud water and their presence is related to the presence of microorganisms. Compounds presenting similarities with high molecular weight organic substances or HULIS found in aerosols were also observed in clouds. Overall, these studies mainly focused on individual compounds or functional groups rather than the complex mixture at the molecular level. This study presents a non-targeted approach to characterize the organic matter in clouds. Samples were collected at the puy de Dôme Mountain (France). Two cloud water samples (June & July 2016) were analyzed using high resolution mass spectrometry (ESI-FT-ICR-MS 9.4T). A reversed solid phase extraction (SPE) procedure was performed to concentrate dissolved organic matter components. Composer (v.1.5.3) software was used to filter the mass spectral data, recalibrate externally the dataset and calculate all possible formulas for detected anions. The first cloud sample (June) resulted from air mass coming from the North (North Sea) while the second one (July) resulted from air mass coming from the West (Atlantic Ocean). Thus, both cloud events derived from marine air masses but were characterized by different hydrogen peroxide concentration and dissolved organic carbon content and were sampled at different periods during the day. Elemental compositions of 6487 and 3284 unique molecular species were identified in each sample. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS & CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with molecular weights up to 800 Da were detected. The main class is CHNO (53% for both samples) while sulfur-containing compounds represent for the two samples respectively 21 & 14% of the total assigned molecular formulas. CHO compounds molecular formulas are respectively 25 & 32%. Among the two samples, only 2490 molecular formulas were found common to the two samples.

Molecular and Imaging Insights into the Formation of Soil Organic Matter in a Red Pine Rhizosphere

NASA Astrophysics Data System (ADS)

Dohnalkova, A.; Tfaily, M.; Smith, A. P.; Chu, R. K.; Crump, A.; Brislawn, C.; Varga, T.; Shi, Z.; Thomashow, L. S.; Harsh, J. B.; Balogh-Brunstad, Z.; Keller, C. K.

2017-12-01

Microbially-derived carbon inputs to soils play an important role in forming soil organic matter (SOM), but detailed knowledge of basic mechanisms of carbon (C) cycling, such as stabilization of organic C compounds originating from rhizodeposition, is limited. The objective of this study aimed to investigate the stability of rhizosphere-produced carbon components in a model laboratory mesocosm of Pinus resinosa grown in a designed mineral soil mix. We hypothesized that nutrient limitation would cause formation of microbially-produced C constituents that would contribute to SOM stabilization. We focused on the processes of rhizodeposition in the rhizosphere, and we utilized a suite of advanced imaging and molecular techniques to obtain a molecular-level identification of the microbial community and the newly-formed SOM compounds in the rhizosphere and the bulk soil. We considered implications regarding their degree of long-term stability. The microbes in this controlled, nutrient-limited system, without pre-existing organic matter, produced extracellular polymeric substances that formed associations with nutrient-bearing minerals and contributed to the microbial mineral weathering process. Electron microscopy revealed unique ultrastructural residual signatures of biogenic C compounds, and the increased presence of an amorphous organic phase associated with the mineral phase was evidenced by X-ray diffraction. These findings provide insight into the various degrees of stability of microbial SOM products in ecosystems and evidence that the residual biogenic material associated with mineral matrices may be important components in current carbon cycle models.

Investigation of extractable organic compounds in deep-sea hydrothermal vent fluids along the Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

McCollom, Thomas M.; Seewald, Jeffrey S.; German, Christopher R.

2015-05-01

The possibility that deep-sea hydrothermal vents may contain organic compounds produced by abiotic synthesis or by microbial communities living deep beneath the surface has led to numerous studies of the organic composition of vent fluids. Most of these studies have focused on methane and other light hydrocarbons, while the possible occurrence of more complex organic compounds in the fluids has remained largely unstudied. To address this issue, the presence of higher molecular weight organic compounds in deep-sea hydrothermal fluids was assessed at three sites along the Mid-Atlantic Ridge that span a range of temperatures (51 to >360 °C), fluid compositions, and host-rock lithologies (mafic to ultramafic). Samples were obtained at several sites within the Lucky Strike, Rainbow, and Lost City hydrothermal fields. Three methods were employed to extract organic compounds for analysis, including liquid:liquid extraction, cold trapping on the walls of a coil of titanium tubing, and pumping fluids through cartridges filled with solid phase extraction (SPE) sorbents. The only samples to consistently yield high amounts of extractable organic compounds were the warm (51-91 °C), highly alkaline fluids from Lost City, which contained elevated concentrations of C8, C10, and C12n-alkanoic acids and, in some cases, trithiolane, hexadecanol, squalene, and cholesterol. Collectively, the C8-C12 acids can account for about 15% of the total dissolved organic carbon in the Lost City fluids. The even-carbon-number predominance of the alkanoic acids indicates a biological origin, but it is unclear whether these compounds are derived from microbial activity occurring within the hydrothermal chimney proximal to the site of fluid discharge or are transported from deeper within the system. Hydrothermal fluids from the Lucky Strike and Rainbow fields were characterized by an overall scarcity of extractable dissolved organic compounds. Trace amounts of aromatic hydrocarbons including phenanthrenes and benzothiophene were the only compounds that could be identified as indigenous components of these fluids. Although hydrocarbons and fatty acids were observed in some samples, those compounds were likely derived from particulate matter or biomass entrained during fluid collection. In addition, extracts of some fluid samples from the Rainbow field were found to contain an unresolved complex mixture (UCM) of organic compounds. This UCM shared some characteristics with organic matter extracted from bottom seawater, suggesting that the organic matter observed in these samples might represent seawater-derived compounds that had persisted, albeit with partial alteration, during circulation through the hydrothermal system. While there is considerable evidence that Rainbow and Lost City vent fluids contain methane and other light hydrocarbons produced through abiotic reduction of inorganic carbon, we found no evidence for more complex organic compounds with an abiotic origin in the same fluids.

Estrogen Receptor Binding Affinity of Food Contact Material Components Estimated by QSAR.

PubMed

Sosnovcová, Jitka; Rucki, Marián; Bendová, Hana

2016-09-01

The presented work characterized components of food contact materials (FCM) with potential to bind to estrogen receptor (ER) and cause adverse effects in the human organism. The QSAR Toolbox, software application designed to identify and fill toxicological data gaps for chemical hazard assessment, was used. Estrogen receptors are much less of a lock-and-key interaction than highly specific ones. The ER is nonspecific enough to permit binding with a diverse array of chemical structures. There are three primary ER binding subpockets, each with different requirements for hydrogen bonding. More than 900 compounds approved as of FCM components were evaluated for their potential to bind on ER. All evaluated chemicals were subcategorized to five groups with respect to the binding potential to ER: very strong, strong, moderate, weak binder, and no binder to ER. In total 46 compounds were characterized as potential disturbers of estrogen receptor. Among the group of selected chemicals, compounds with high and even very high affinity to the ER binding subpockets were found. These compounds may act as gene activators and cause adverse effects in the organism, particularly during pregnancy and breast-feeding. It should be considered to carry out further in vitro or in vivo tests to confirm their potential to disturb the regulation of physiological processes in humans by abnormal ER signaling and subsequently remove these chemicals from the list of approved food contact materials. Copyright© by the National Institute of Public Health, Prague 2016

Synthesis, characterization and air stable semiconductor properties of thiophene-condensed pyrene derivatives

NASA Astrophysics Data System (ADS)

Moriguchi, Tetsuji; Higashi, Makoto; Yakeya, Daisuke; Jalli, Venkataprasad; Tsuge, Akihiko; Okauchi, Tatsuo; Nagamatsu, Shuichi; Takashima, Wataru

2017-01-01

New and simple polyaromatic compounds containing two thiophene rings were prepared via photo-cyclization and their structural and photophysical properties were evaluated via 1H NMR spectroscopy and X-ray crystallographic analysis. On the basis of X-ray analysis, it was determined that the molecular structure of the compound was highly strained and that they contain two hetero [4] helicene moieties. The compounds were investigated as active layer in p-type organic field-effect transistors (p-OFET) in top contact type devices. Notably, the compound containing two thiophene components exhibited very stable p-type semiconducting behavior in moist air.

Identification of volatiles from the secretions and excretions of African wild dogs (Lycaon pictus).

PubMed

Apps, Peter; Mmualefe, Lesego; McNutt, J Weldon

2012-11-01

Gas chromatography/mass spectrometry was used to identify 103 organic compounds from urine, feces, anal glands, and preputial glands of free-ranging African wild dogs, Lycaon pictus. Aliphatic acids were the dominant class of compound in all materials. In addition to aliphatic acids, urine contained dimethyl sulfone, 1,3-propanediol, benzoic acid, 1-methyl-2,4-imidazolidinedione, and squalene as major components: feces contained indole and cholesterol; and both contained 2-piperidone, phenol, 4-methyl phenol, benzeneacetic acid, and benzenepropanoic acid and other compounds. Anal gland secretion was particularly rich in cholesterol and fatty acids, and preputial gland secretion rich in squalene. A large majority of the identified compounds have been reported from other mammals, including species sympatric with African wild dogs. Eleven of the African wild dog components have not been reported previously from mammals and have not been found in sympatric species; one component, 1-methylimidazole-5-carboxaldehyde has not been reported previously as a natural product. In the chemical profiles of their urine, feces, and anal gland secretion African wild dogs differ markedly from other canids.

Metallic elements in fossil fuel combustion products: amounts and form of emissions and evaluation of carcinogenicity and mutagenicity.

PubMed

Vouk, V B; Piver, W T

1983-01-01

Metallic elements contained in coal, oil and gasoline are mobilized by combustion processes and may be emitted into the atmosphere, mainly as components of submicron particles. The information about the amounts, composition and form of metal compounds is reviewed for some fuels and combustion processes. Since metal compounds are always contained in urban air pollutants, they have to be considered whenever an evaluation of biological impact of air pollutants is made. The value of currently used bioassays for the evaluation of the role of trace metal compounds, either as major biologically active components or as modifiers of biological effects of organic compounds is assessed. The whole animal bioassays for carcinogenicity do not seem to be an appropriate approach. They are costly, time-consuming and not easily amenable to the testing of complex mixtures. Some problems related to the application and interpretation of short-term bioassays are considered, and the usefulness of such bioassays for the evaluation of trace metal components contained in complex air pollution mixtures is examined.

Metallic elements in fossil fuel combustion products: amounts and form of emissions and evaluation of carcinogenicity and mutagenicity.

PubMed Central

Vouk, V B; Piver, W T

1983-01-01

Metallic elements contained in coal, oil and gasoline are mobilized by combustion processes and may be emitted into the atmosphere, mainly as components of submicron particles. The information about the amounts, composition and form of metal compounds is reviewed for some fuels and combustion processes. Since metal compounds are always contained in urban air pollutants, they have to be considered whenever an evaluation of biological impact of air pollutants is made. The value of currently used bioassays for the evaluation of the role of trace metal compounds, either as major biologically active components or as modifiers of biological effects of organic compounds is assessed. The whole animal bioassays for carcinogenicity do not seem to be an appropriate approach. They are costly, time-consuming and not easily amenable to the testing of complex mixtures. Some problems related to the application and interpretation of short-term bioassays are considered, and the usefulness of such bioassays for the evaluation of trace metal components contained in complex air pollution mixtures is examined. PMID:6337825

Organic matter in meteorites and comets - Possible origins

NASA Technical Reports Server (NTRS)

Anders, Edward

1991-01-01

At least six extraterrestrial environments may have contributed organic compounds to meteorites and comets: solar nebula, giant-planet subnebulae, asteroid interiors containing liquid water, carbon star atmospheres, and diffuse or dark interstellar clouds. The record in meteorites is partly obscured by pervasive reheating that transformed much of the organic matter to kerogen; nonetheless, it seems that all six formation sites contributed. For comets, the large abundance of HCHO, HCN, and unsaturated hydrocarbons suggests an interstellar component of 50 percent or more, but the contributions of various interstellar processes, and of a solar-nebula component, are hard to quantify. A research program is outlined that may help reduce these uncertainties.

Sensitivity of Aerosol Mass and Microphysics to varying treatments of Condensational Growth of Secondary Organic Compounds in a regional model

NASA Astrophysics Data System (ADS)

Lowe, Douglas; Topping, David; McFiggans, Gordon

2017-04-01

Gas to particle partitioning of atmospheric compounds occurs through disequilibrium mass transfer rather than through instantaneous equilibrium. However, it is common to treat only the inorganic compounds as partitioning dynamically whilst organic compounds, represented by the Volatility Basis Set (VBS), are partitioned instantaneously. In this study we implement a more realistic dynamic partitioning of organic compounds in a regional framework and assess impact on aerosol mass and microphysics. It is also common to assume condensed phase water is only associated with inorganic components. We thus also assess sensitivity to assuming all organics are hygroscopic according to their prescribed molecular weight. For this study we use WRF-Chem v3.4.1, focusing on anthropogenic dominated North-Western Europe. Gas-phase chemistry is represented using CBM-Z whilst aerosol dynamics are simulated using the 8-section MOSAIC scheme, including a 9-bin VBS treatment of organic aerosol. Results indicate that predicted mass loadings can vary significantly. Without gas phase ageing of higher volatility compounds, dynamic partitioning always results in lower mass loadings downwind of emission sources. The inclusion of condensed phase water in both partitioning models increases the predicted PM mass, resulting from a larger contribution from higher volatility organics, if present. If gas phase ageing of VBS compounds is allowed to occur in a dynamic model, this can often lead to higher predicted mass loadings, contrary to expected behaviour from a simple non-reactive gas phase box model. As descriptions of aerosol phase processes improve within regional models, the baseline descriptions of partitioning should retain the ability to treat dynamic partitioning of organics compounds. Using our simulations, we discuss whether derived sensitivities to aerosol processes in existing models may be inherently biased. This work was supported by the Natural Environment Research Council within the RONOCO (NE/F004656/1) and CCN-Vol (NE/L007827/1) projects.

Sensitivity of Aerosol Mass and Microphysics to Treatments of Condensational Growth of Secondary Organic Compounds in a Regional Model

NASA Astrophysics Data System (ADS)

Topping, D. O.; Lowe, D.; McFiggans, G.; Zaveri, R. A.

2016-12-01

Gas to particle partitioning of atmospheric compounds occurs through disequilibrium mass transfer rather than through instantaneous equilibrium. However, it is common to treat only the inorganic compounds as partitioning dynamically whilst organic compounds, represented by the Volatility Basis Set (VBS), are partitioned instantaneously. In this study we implement a more realistic dynamic partitioning of organic compounds in a regional framework and assess impact on aerosol mass and microphysics. It is also common to assume condensed phase water is only associated with inorganic components. We thus also assess sensitivity to assuming all organics are hygroscopic according to their prescribed molecular weight.For this study we use WRF-Chem v3.4.1, focusing on anthropogenic dominated North-Western Europe. Gas-phase chemistry is represented using CBM-Z whilst aerosol dynamics are simulated using the 8-section MOSAIC scheme, including a 9-bin volatility basis set (VBS) treatment of organic aerosol. Results indicate that predicted mass loadings can vary significantly. Without gas phase ageing of higher volatility compounds, dynamic partitioning always results in lower mass loadings downwind of emission sources. The inclusion of condensed phase water in both partitioning models increases the predicted PM mass, resulting from a larger contribution from higher volatility organics, if present. If gas phase ageing of VBS compounds is allowed to occur in a dynamic model, this can often lead to higher predicted mass loadings, contrary to expected behaviour from a simple non-reactive gas phase box model. As descriptions of aerosol phase processes improve within regional models, the baseline descriptions of partitioning should retain the ability to treat dynamic partitioning of organic compounds. Using our simulations, we discuss whether derived sensitivities to aerosol processes in existing models may be inherently biased.This work was supported by the Nature Environment Research Council within the RONOCO (NE/F004656/1) and CCN-Vol (NE/L007827/1) projects.

Needle Trap Device as a New Sampling and Preconcentration Approach for Volatile Organic Compounds of Herbal Medicines and its Application to the Analysis of Volatile Components in Viola tianschanica.

PubMed

Qin, Yan; Pang, Yingming; Cheng, Zhihong

2016-11-01

The needle trap device (NTD) technique is a new microextraction method for sampling and preconcentration of volatile organic compounds (VOCs). Previous NTD studies predominantly focused on analysis of environmental volatile compounds in the gaseous and liquid phases. Little work has been done on its potential application in biological samples and no work has been reported on analysis of bioactive compounds in essential oils from herbal medicines. The main purpose of the present study is to develop a NTD sampling method for profiling VOCs in biological samples using herbal medicines as a case study. A combined method of NTD sample preparation and gas chromatography-mass spectrometry was developed for qualitative analysis of VOCs in Viola tianschanica. A 22-gauge stainless steel, triple-bed needle packed with Tenax, Carbopack X and Carboxen 1000 sorbents was used for analysis of VOCs in the herb. Furthermore, different parameters affecting the extraction efficiency and capacity were studied. The peak capacity obtained by NTDs was 104, more efficient than those of the static headspace (46) and hydrodistillation (93). This NTD method shows potential to trap a wide range of VOCs including the lower and higher volatile components, while the static headspace and hydrodistillation only detects lower volatile components, and semi-volatile and higher volatile components, respectively. The developed NTD sample preparation method is a more rapid, simpler, convenient, and sensitive extraction/desorption technique for analysis of VOCs in herbal medicines than the conventional methods such as static headspace and hydrodistillation. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Design Your Own Workup: A Guided-Inquiry Experiment for Introductory Organic Laboratory Courses

ERIC Educational Resources Information Center

Mistry, Nimesh; Fitzpatrick, Christopher; Gorman, Stephen

2016-01-01

A guided-inquiry experiment was designed and implemented in an introductory organic chemistry laboratory course. Students were given a mixture of compounds and had to isolate two of the components by designing a viable workup procedure using liquid-liquid separation methods. Students were given the opportunity to apply their knowledge of chemical…

Profiling Taste and Aroma Compound Metabolism during Apricot Fruit Development and Ripening

PubMed Central

Xi, Wanpeng; Zheng, Huiwen; Zhang, Qiuyun; Li, Wenhui

2016-01-01

Sugars, organic acids and volatiles of apricot were determined by HPLC and GC-MS during fruit development and ripening, and the key taste and aroma components were identified by integrating flavor compound contents with consumers’ evaluation. Sucrose and glucose were the major sugars in apricot fruit. The contents of all sugars increased rapidly, and the accumulation pattern of sugars converted from glucose-predominated to sucrose-predominated during fruit development and ripening. Sucrose synthase (SS), sorbitol oxidase (SO) and sorbitol dehydrogenase (SDH) are under tight developmental control and they might play important roles in sugar accumulation. Almost all organic acids identified increased during early development and then decrease rapidly. During early development, fruit mainly accumulated quinate and malate, with the increase of citrate after maturation, and quinate, malate and citrate were the predominant organic acids at the ripening stage. The odor activity values (OAV) of aroma volatiles showed that 18 aroma compounds were the characteristic components of apricot fruit. Aldehydes and terpenes decreased significantly during the whole development period, whereas lactones and apocarotenoids significantly increased with fruit ripening. The partial least squares regression (PLSR) results revealed that β-ionone, γ-decalactone, sucrose and citrate are the key characteristic flavor factors contributing to consumer acceptance. Carotenoid cleavage dioxygenases (CCD) may be involved in β-ionone formation in apricot fruit. PMID:27347931

Functional involvement of the organic cation transporter 2 (rOct2) in the renal uptake of organic cations in rats.

PubMed

Umehara, K-I; Iwatsubo, T; Noguchi, K; Kamimura, H

2008-01-01

This study examined the contribution made by organic cation transporters (hOCT/rOct) to the saturable component of the renal uptake of 1-methyl-4-phenylpyridinium, tetraethylammonium (TEA), cimetidine and metformin into rOct2-expressing HEK293 cells and rat kidney slices. All the test compounds accumulated in the rat kidney slices in a carrier-mediated manner. The Michaelis- Menten constant (K(m)) values for saturable uptake of TEA, cimetidine and metformin into rat kidney slices were relatively comparable with those for the rOct2-expressing HEK293 cells. In addition, the relative uptake activity values of TEA, cimetidine and metformin in rat kidney slices were similar to those in rOct2-expressing HEK293 cells. This suggests that the saturable components involved in the renal uptake of TEA, cimetidine and metformin are mediated mainly by rOct2. The saturable uptake profile of cationic compounds into rat kidney can be evaluated in both cDNA-expressing cells and rat kidney slices, as well as the transporter expression pattern. This approach can also be used to estimate the saturable uptake mechanism of cationic compounds into the human kidney when human kidney slices and hOCT2-expressing cells are used.

Classifying organic materials by oxygen-to-carbon elemental ratio to predict the activation regime of cloud condensation nuclei (CCN)

NASA Astrophysics Data System (ADS)

Kuwata, M.; Shao, W.; Lebouteiller, R.; Martin, S. T.

2012-12-01

The governing highly soluble, slightly soluble, or insoluble activation regime of organic compounds as cloud condensation nuclei (CCN) was examined as a function of oxygen-to-carbon elemental ratio (O : C). New data were collected for adipic, pimelic, suberic, azelaic and pinonic acids. Secondary organic materials (SOMs) produced by α-pinene ozonolysis and isoprene photo-oxidation were also included in the analysis. The saturation concentrations C of the organic compounds in aqueous solutions served as the key parameter for delineating regimes of CCN activation, and the values of C were tightly correlated to the O : C ratios. The highly soluble, slightly soluble, and insoluble regimes of CCN activation were found to correspond to ranges of [O : C] > 0.6, 0.2 < [O : C] < 0.6, and [O : C] < 0.2, respectively. These classifications were evaluated against CCN activation data of isoprene-derived SOM (O : C = 0.69-0.72) and α-pinene-derived SOM (O : C = 0.38-0.48). Isoprene-derived SOM had highly soluble activation behavior, consistent with its high O : C ratio. For α-pinene-derived SOM, although CCN activation can be modeled as a highly soluble mechanism, this behavior was not predicted by the O : C ratio, for which a slightly soluble mechanism was anticipated. Complexity in chemical composition, resulting in continuous water uptake and the absence of a deliquescence transition that can thermodynamically limit CCN activation, might explain the differences of α-pinene-derived SOM compared to the behavior of pure organic compounds. The present results suggest that atmospheric particles dominated by hydrocarbon-like organic components do not activate (i.e. insoluble regime) whereas those dominated by oxygenated organic components activate (i.e. highly soluble regime).

Classifying organic materials by oxygen-to-carbon elemental ratio to predict the activation regime of Cloud Condensation Nuclei (CCN)

NASA Astrophysics Data System (ADS)

Kuwata, M.; Shao, W.; Lebouteiller, R.; Martin, S. T.

2013-05-01

The governing highly soluble, slightly soluble, or insoluble activation regime of organic compounds as cloud condensation nuclei (CCN) was examined as a function of oxygen-to-carbon elemental ratio (O : C). New data were collected for adipic, pimelic, suberic, azelaic, and pinonic acids. Secondary organic materials (SOMs) produced by α-pinene ozonolysis and isoprene photo-oxidation were also included in the analysis. The saturation concentrations C of the organic compounds in aqueous solutions served as the key parameter for delineating regimes of CCN activation, and the values of C were tightly correlated to the O : C ratios. The highly soluble, slightly soluble, and insoluble regimes of CCN activation were found to correspond to ranges of [O : C] > 0.6, 0.2 < [O : C] < 0.6, and [O : C] < 0.2, respectively. These classifications were evaluated against CCN activation data of isoprene-derived SOM (O : C = 0.69-0.72) and α-pinene-derived SOM (O : C = 0.38-0.48). Isoprene-derived SOM had highly soluble activation behavior, consistent with its high O : C ratio. For α-pinene-derived SOM, although CCN activation can be modeled as a highly soluble mechanism, this behavior was not predicted by the O : C ratio, for which a slightly soluble mechanism was anticipated. Complexity in chemical composition, resulting in continuous water uptake and the absence of a deliquescence transition that can thermodynamically limit CCN activation, might explain the difference in the behavior of α-pinene-derived SOM compared to that of pure organic compounds. The present results suggest that atmospheric particles dominated by hydrocarbon-like organic components do not activate (i.e., insoluble regime) whereas those dominated by oxygenated organic components activate (i.e., highly soluble regime) for typical atmospheric cloud life cycles.

Slow aging in Secondary Organic Aerosol observed by Liquid Chromatography coupled with High-Resolution Mass Spectrometry

NASA Astrophysics Data System (ADS)

Bones, D. L.; Bateman, A. P.; Nguyen, T. B.; Laskin, J.; Laskin, A.; Nizkorodov, S.

2009-12-01

This study investigated long term changes in the chemical composition of model biogenic secondary organic aerosol (SOA) prepared via ozonolysis of the terpene limonene. This SOA has been observed to turn brown when exposed to NH4+. Our hypothesis is that the chromophoric compounds responsible for this color change are suspected to be imidazole-like or pyridinium-like compounds. These compounds are only present in small relative amounts, hence standard mass spectrometry is insufficient to unambiguously detect these compounds. However, a combination of HPLC and high resolution electrospray ionization mass spectrometry allows assignments of chemical formulae to individual peaks. These and other experiments confirm the presence of N-containing compounds in treated SOA. We are in the process of determining the exact identity of these species by MS/MS methods. LC-MS can also provide information about the polarity of the compounds in SOA. Most compounds in limonene-O3 SOA are polar and are detected at short retention times; peaks suggesting trimeric species appear at longer retention times in the case of fresh SOA, but at shorter times with the bulk of the components for aged SOA. Limonene SOA has been shown to be composed of monomers, dimers, trimers and larger oligomers. The appearance of trimers in specific regions of the chromatogram suggests these species are genuine SOA components and not an artifact of electrospray ionization. Changes in biogenic SOA over time are important because of the propensity of SOA to affect direct and indirect radiative forcing.

Solid-phase extraction versus matrix solid-phase dispersion: Application to white grapes.

PubMed

Dopico-García, M S; Valentão, P; Jagodziñska, A; Klepczyñska, J; Guerra, L; Andrade, P B; Seabra, R M

2007-11-15

The use of matrix solid-phase dispersion (MSPD) was tested to, separately, extract phenolic compounds and organic acids from white grapes. This method was compared with a more conventional analytical method previously developed that combines solid liquid extraction (SL) to simultaneously extract phenolic compounds and organic acids followed by a solid-phase extraction (SPE) to separate the two types of compounds. Although the results were qualitatively similar for both techniques, the levels of extracted compounds were in general quite lower on using MSPD, especially for organic acids. Therefore, SL-SPE method was preferred to analyse white "Vinho Verde" grapes. Twenty samples of 10 different varieties (Alvarinho, Avesso, Asal-Branco, Batoca, Douradinha, Esganoso de Castelo Paiva, Loureiro, Pedernã, Rabigato and Trajadura) from four different locations in Minho (Portugal) were analysed in order to study the effects of variety and origin on the profile of the above mentioned compounds. Principal component analysis (PCA) was applied separately to establish the main sources of variability present in the data sets for phenolic compounds, organic acids and for the global data. PCA of phenolic compounds accounted for the highest variability (77.9%) with two PCs, enabling characterization of the varieties of samples according to their higher content in flavonol derivatives or epicatechin. Additionally, a strong effect of sample origin was observed. Stepwise linear discriminant analysis (SLDA) was used for differentiation of grapes according to the origin and variety, resulting in a correct classification of 100 and 70%, respectively.

Major structural components in freshwater dissolved organic matter.

PubMed

Lam, Buuan; Baer, Andrew; Alaee, Mehran; Lefebvre, Brent; Moser, Arvin; Williams, Antony; Simpson, André J

2007-12-15

Dissolved organic matter (DOM) contains a complex array of chemical components that are intimately linked to many environmental processes, including the global carbon cycle, and the fate and transport of chemical pollutants. Despite its importance, fundamental aspects, such as the structural components in DOM remain elusive, due in part to the molecular complexity of the material. Here, we utilize multidimensional nuclear magnetic resonance spectroscopy to demonstrate the major structural components in Lake Ontario DOM. These include carboxyl-rich alicyclic molecules (CRAM), heteropolysaccharides, and aromatic compounds, which are consistent with components recently identified in marine dissolved organic matter. In addition, long-range proton-carbon correlations are obtained for DOM, which support the existence of material derived from linear terpenoids (MDLT). It is tentatively suggested that the bulk of freshwater dissolved organic matter is aliphatic in nature, with CRAM derived from cyclic terpenoids, and MDLT derived from linear terpenoids. This is in agreement with previous reports which indicate terpenoids as major precursors of DOM. At this time it is not clear in Lake Ontario whether these precursors are of terrestrial or aquatic origin or whether transformations proceed via biological and/ or photochemical processes.

Chemical fingerprinting of naphthenic acids and oil sands process waters-A review of analytical methods for environmental samples.

PubMed

Headley, J V; Peru, K M; Mohamed, M H; Frank, R A; Martin, J W; Hazewinkel, R R O; Humphries, D; Gurprasad, N P; Hewitt, L M; Muir, D C G; Lindeman, D; Strub, R; Young, R F; Grewer, D M; Whittal, R M; Fedorak, P M; Birkholz, D A; Hindle, R; Reisdorph, R; Wang, X; Kasperski, K L; Hamilton, C; Woudneh, M; Wang, G; Loescher, B; Farwell, A; Dixon, D G; Ross, M; Pereira, A Dos Santos; King, E; Barrow, M P; Fahlman, B; Bailey, J; McMartin, D W; Borchers, C H; Ryan, C H; Toor, N S; Gillis, H M; Zuin, L; Bickerton, G; Mcmaster, M; Sverko, E; Shang, D; Wilson, L D; Wrona, F J

2013-01-01

This article provides a review of the routine methods currently utilized for total naphthenic acid analyses. There is a growing need to develop chemical methods that can selectively distinguish compounds found within industrially derived oil sands process affected waters (OSPW) from those derived from the natural weathering of oil sands deposits. Attention is thus given to the characterization of other OSPW components such as oil sands polar organic compounds, PAHs, and heavy metals along with characterization of chemical additives such as polyacrylamide polymers and trace levels of boron species. Environmental samples discussed cover the following matrices: OSPW containments, on-lease interceptor well systems, on- and off-lease groundwater, and river and lake surface waters. There are diverse ranges of methods available for analyses of total naphthenic acids. However, there is a need for inter-laboratory studies to compare their accuracy and precision for routine analyses. Recent advances in high- and medium-resolution mass spectrometry, concomitant with comprehensive mass spectrometry techniques following multi-dimensional chromatography or ion-mobility separations, have allowed for the speciation of monocarboxylic naphthenic acids along with a wide range of other species including humics. The distributions of oil sands polar organic compounds, particularly the sulphur containing species (i.e., OxS and OxS2) may allow for distinguishing sources of OSPW. The ratios of oxygen- (i.e., Ox) and nitrogen-containing species (i.e., NOx, and N2Ox) are useful for differentiating organic components derived from OSPW from natural components found within receiving waters. Synchronous fluorescence spectroscopy also provides a powerful screening technique capable of quickly detecting the presence of aromatic organic acids contained within oil sands naphthenic acid mixtures. Synchronous fluorescence spectroscopy provides diagnostic profiles for OSPW and potentially impacted groundwater that can be compared against reference groundwater and surface water samples. Novel applications of X-ray absorption near edge spectroscopy (XANES) are emerging for speciation of sulphur-containing species (both organic and inorganic components) as well as industrially derived boron-containing species. There is strong potential for an environmental forensics application of XANES for chemical fingerprinting of weathered sulphur-containing species and industrial additives in OSPW.

Dual role of preputial gland secretion and its major components in sex recognition of mice.

PubMed

Zhang, Jian-Xu; Liu, Ying-Juan; Zhang, Jin-Hua; Sun, Lixing

2008-10-20

This study was aimed at validating the sexual attractiveness of hexadecanol and hexadecyl acetate, two putative pheromone compounds, from preputial gland secretion of mice. These two compounds have been reported to be among the major components of preputial gland secretion in both sexes but higher in quantity in males than females. In this study, we show that castration suppressed the production of the two compounds, further suggesting their association with maleness. Adding preputial gland secretion and the synthetic analogs of the two compounds to castrated male urine at their physiological levels in intact males increased the attractiveness of castrated male urine to female mice, showing that the two compounds were indeed male pheromones. Furthermore, their sexual attractiveness disappeared upon removing the vomeronasal organs (VNOs) from female recipients. Replenishing castrated male urine with preputial gland secretion and the two compounds at their physiological levels in females increased the attractiveness of castrated male urine to males. Such a reversal of sexual attractiveness for hexadecanol and hexadecyl acetate suggests that they had opposing dual effects in sexual attractiveness in a dosage-dependent manner.

On the Chemical Characterization of Organic Matter in Rain at Mexico City.

NASA Astrophysics Data System (ADS)

Montero-Martinez, G.; Andraca-Ayala, G. L.; Hernández-Nagay, D. P.; Mendoza-Trejo, A.; Rivera-Arellano, J.; Rosado-Abon, A.; Roy, P. D.

2016-12-01

The chemical composition of the aerosol plays a central role in atmospheric processes and has influence on the hydrological cycle. Clouds form through the nucleation of water vapor on certain atmospheric aerosol particles, called cloud condensation nuclei (CCN). Also, precipitating particles scavenge some other aerosol particles on their way to the surface. Atmospheric particles are a mixture of organic and inorganic materials, both soluble and insoluble in water. Aerosol chemical characterization indicates a larger variety of compounds in urban areas respect to other regions. Thus, chemical composition of rainwater may represent an important aspect for estimating atmospheric air pollution. It has been recognized that organic species present in aerosol particles are important in the formation of cloud droplets. Therefore, the information about the organic compounds in precipitation samples may be helpful to understand their effects on the formation of clouds and rain, as well as their sources. Organic acids are ubiquitous components of aerosols and have been identified in precipitation water. In this work, preliminary results of the content of soluble organic (neutral and acidic) matter in rainwater samples collected in Mexico City during 2015 will be presented. The organic compounds content was performed by using an ionic chromatographic methodology with gradient elution; so the total amount was evaluated as the sum of four fractions: neutral/basic, mono-, bi-, and poly-acid compounds. The outcomes suggest that most of the amount of organic substances soluble in water is contained by the neutral/basic and mono-acid fractions. Regarding the total amount of water soluble organic compounds, the rain samples collected in Mexico City are in agreement with some others reported for large urban areas.

Optimization of conditions for thermal treatment of rice bran using an accelerator including an organo-iron compound.

PubMed

Kanno, Hikari; Tachibana, Naoya; Fukushima, Masami

2011-02-01

A method for thermal conversion of raw organic waste (ROW) to a compost-like material (CLM) with higher levels of unsaturated carbohydrates, nitrogen- and oxygen-containing compounds was developed, in which rice bran and an organo-iron compound were employed as a model ROW and the accelerator, respectively. To evaluate the qualities of CLMs, organic substances of an acid insoluble fraction of alkaline extracts (AIAEs) from a CLM were structurally characterized by elemental analysis, pyrolysis-gas chromatography/mass spectrometry and FT-IR. The levels of unsaturated carbohydrates, and nitrogen- and oxygen-containing compounds in the CLM samples were increased by long-term treatment (60°C for 5 days, 170°C for 3 days). In particular, the high lipid content of the AIAEs, which was indicative of inadequate digestion of CLM components, was dramatically reduced in the presence of the accelerator. Copyright © 2010 Elsevier Ltd. All rights reserved.

Biotransformation of an uncured composite material

NASA Technical Reports Server (NTRS)

Welsh, Clement J.; Glass, Michael J.; Cheslack, Brian; Pryor, Robert; Tran, Duan K.; Bowers-Irons, Gail

1994-01-01

The feasibility of biologically degrading prepreg wastes was studied. The work was conducted with the intention of obtaining baseline data that would facilitate the achievement of two long-range goals. These goals are: (1) the biological remediation of the hazardous components in the prepreg wastes, and (2) providing the potential for recycling the prepreg waste fibers. The experiments examined a prepreg that employs an bismaleimide resin system. Initial results demonstrated an obvious deterioration of the prepreg material when incubated with several bacterial strains. The most active cultures were identified as a mixture of 'Bacillus cereus' and 'Pseudomonas sp'. Gas chromatography analyses revealed seven primary compounds in the resin mixture. Biotransformation studies, using the complete prepreg material, demonstrated on obvious loss of all seven organic compounds. Gas chromatography-mass spectrometry analyses resulted in structure assignments for the two primary components of the resin. Both were analogs of Bisphenol A; one being bismaleimide, and the other being Bisphenol A containing a diglycidyl moiety. The 'diglycidyl analog' was purified using thin-layer chromatography and the biotransformation of this compound (at 27 ug/ml bacterial culture) was monitored. After a seven-day incubation, approximately 40% of the organic compound was biotransformed. These results demonstrate the biotransformation of the prepreg resin and indicate that biological remediation of the prepreg wastes is feasible.

Impact of tree cutting on water-soluble organic compounds in podzolic soils of the European North-East

NASA Astrophysics Data System (ADS)

Lapteva, Elena; Bondarenko, Natalia; Shamrikova, Elena; Kubik, Olesya; Punegov, Vasili

2016-04-01

Water-soluble organic compounds (WOCs) and their single components, i.e. low-molecular organic acids, alcohols, and carbohydrates, attain a great deal of attention among soil scientists. WOCs are an important component of soil organic matter (SOM) and form as a results of different biological and chemical processes in soils. These processes are mainly responsible for formation and development of soils in aboveground ecosystems. The purpose of the work was identifying qualitative and quantitative composition of low-molecular organic substances which form in podzolic loamy soils against natural reforestation after spruce forest cutting. The studies were conducted on the territory of the European North-East of Russia, in the middle taiga subzone (Komi Republic, Ust-Kulom region). The study materials were soil of undisturbed bilberry spruce forest (Sample Plot 1 (SP1)) and soils of different-aged tree stands where cutting activities took place in winter 2001/2002 (SP2) and 1969/1970 (SP3). Description of soils and vegetation cover on the plots is given in [1]. Low-molecular organic compounds in soil water extracts were identified by the method of gas chromatography mass-spectrometry [2, 3]. Finally, reforestationafterspruceforestcutting was found to be accompanied by different changes in soil chemical composition. In contrast with soils under undisturbed spruce forest, organic soil horizons under different-aged cuts decreased in organic carbon reserves and production of low-molecular organic compounds, changed in soil acidity. Within the soil series of SP1→SP2→SP3, the highest content of WOCs was identified for undisturbed spruce forest (738 mg kg-1 soil). In soils of coniferous-deciduous forests on SP1 and SP3, WOC content was 294 and 441 mg kg-1 soil, correspondingly. Soils at cuts decreased in concentration of any water-soluble low-molecular SOM components as low-molecular acids, alcohols, and carbohydrates. Structure of low-molecular WOCs in the study podzolic soils was dominated by carbohydrates with ratio from 49% (SP1) to 63-66% (SP2, SP3) of total content of all identified compounds. The increase in relative content in carbohydrates observed for soils under cuts was possibly affected by vegetation cover change after clear-cutting and presence of birch and aspen leaves in plant waste composition (due to tree species change). At SP2 and SP3 cuts, content of alcohols and low-molecular carboxylic acids fell by almost twice as compared with SP1. Tree cuts changed not only in total content of water-soluble compounds but also in ratio of individual low-molecular compounds in water extracts composition. Totally, we identified 26 various compounds, including 12 low-molecular organic (carboxylic) acids, 10 carbohydrates, and 4 alcohols. Composition of carboxylic acids was dominated by aliphatic substituted acids (mainly 2-oxyacetic acid, 2-oxypropane, and 2,3-dioxypropane acids). Total number of aliphatic substituted acids, as well as aliphatic non-substituted and aromatic carboxylic acids, decreased in soils under cuts at initial reforestation stages (SP2). Content of all mentioned acids gradually rose with time (SP3). Soils under cut forests were observed for a decrease of erythrite ratio in composition of water-soluble alcohols (from 52 to 40% of total alcohols) and an increase of glycerin ratio (from 46 to 72%). 10 of identified mono- and disaccharides were dominated by mannose, galactopyranose, and D-ribose. Disturbed soils were identified for increased ratio of galactopyranose and D-ribose and for by almost twice as decreased ratio of mannose. References 1. Dymov, A. A. Changes in the organic matter of taiga soils during the natural reaforestation after cutting in the middle taigaof the Komi Republic / A. A. Dymov, E. Yu. Milanovskii // Eurasian Soil Science, 2013. Vol. 46. № 12. P. 1164-1171. 2. Shamrikova E.V., Punegov V.V., Gruzdev I.V., Vanchikova E.V., Vetoshkina A.A. Individual organic compounds in water extracts from podzolic soils of the Komi Republic // Eurasian Soil Science, 2012. T. 45. № 10. C. 939-946. 3. Shamrikova E.V., Gruzdev I.V., Punegov V.V., Khabibullina F.M., Kubik O.S. Water-soluble low-molecular-weight organic acids in automorphic loamy soils of the tundra and taiga zones // Eurasian Soil Science, 2013. T. 46.№ 6. C. 654-659.

Organics and nitrogen removal from textile auxiliaries wastewater with A2O-MBR in a pilot-scale.

PubMed

Sun, Faqian; Sun, Bin; Hu, Jian; He, Yangyang; Wu, Weixiang

2015-04-09

The removal of organic compounds and nitrogen in an anaerobic-anoxic-aerobic membrane bioreactor process (A(2)O-MBR) for treatment of textile auxiliaries (TA) wastewater was investigated. The results show that the average effluent concentrations of chemical oxygen demand (COD), ammonium nitrogen (NH4(+)-N) and total nitrogen (TN) were about 119, 3 and 48 mg/L under an internal recycle ratio of 1.5. The average removal efficiency of COD, NH4(+)-N and TN were 87%, 96% and 55%, respectively. Gas chromatograph-mass spectrometer analysis indicated that, although as much as 121 different types of organic compounds were present in the TA wastewater, only 20 kinds of refractory organic compounds were found in the MBR effluent, which could be used as indicators of effluents from this kind of industrial wastewater. Scanning electron microscopy analysis revealed that bacterial foulants were significant contributors to membrane fouling. An examination of foulants components by wavelength dispersive X-ray fluorescence showed that the combination of organic foulants and inorganic compounds enhanced the formation of gel layer and thus caused membrane fouling. The results will provide valuable information for optimizing the design and operation of wastewater treatment system in the textile industry. Copyright © 2015 Elsevier B.V. All rights reserved.

Fast detection and characterization of organic and inorganic gunshot residues on the hands of suspects by CMV-GC-MS and LIBS.

PubMed

Tarifa, Anamary; Almirall, José R

2015-05-01

A rapid method for the characterization of both organic and inorganic components of gunshot residues (GSR) is proposed as an alternative tool to facilitate the identification of a suspected shooter. In this study, two fast screening methods were developed and optimized for the detection of organic compounds and inorganic components indicative of GSR presence on the hands of shooters and non-shooters. The proposed methods consist of headspace extraction of volatile organic compounds using a capillary microextraction of volatiles (CMV) device previously reported as a high-efficiency sampler followed by detection by GC-MS. This novel sampling technique has the potential to yield fast results (<2min sampling) and high sensitivity capable of detecting 3ng of diphenylamine (DPA) and 8ng of nitroglycerine (NG). Direct analysis of the headspace of over 50 swabs collected from the hands of suspected shooters (and non-shooters) provides information regarding VOCs present on their hands. In addition, a fast laser induced breakdown spectroscopy (LIBS) screening method for the detection of the inorganic components indicative of the presence of GSR (Sb, Pb and Ba) is described. The sampling method for the inorganics consists of liquid extraction of the target elements from the same cotton swabs (previously analyzed for VOCs) and an additional 30 swab samples followed by spiking 1μL of the extract solution onto a Teflon disk and then analyzed by LIBS. Advantages of LIBS include fast analysis (~12s per sample) and high selectivity and sensitivity, with expected LODs 0.1-18ng for each of the target elements after sampling. The analytical performance of the LIBS method is also compared to previously reported methods (inductively coupled plasma-optical emission spectroscopy). The combination of fast CMV sampling, unambiguous organic compound identification with GC-MS and fast LIBS analysis provides the basis for a new comprehensive screening method for GSR. Copyright © 2015 Forensic Science Society. Published by Elsevier Ireland Ltd. All rights reserved.

Age-dependent changes from allylphenol to prenylated benzoic acid production in Piper gaudichaudianum Kunth.

PubMed

Gaia, Anderson M; Yamaguchi, Lydia F; Jeffrey, Christopher S; Kato, Massuo J

2014-10-01

HPLC-DAD and principal component analysis (PCA) of the (1)H NMR spectrum of crude plant extracts showed high chemical variability among seedlings and adult organs of Piper gaudichaudianum. While gaudichaudianic acid was the major compound in the adult leaves, apiole and dillapiole were the major compounds in their seedling leaves. By the 15th month of seedling growth, the levels of apiole and dillapiole decreased and gaudichaudianic acid appeared along with two compounds, biosynthetically related to gaudichaudianic acid. Copyright © 2014 Elsevier Ltd. All rights reserved.

Characterization of Natural Organic Matter by FeCl3 Coagulation

NASA Astrophysics Data System (ADS)

Cahyonugroho, O. H.; Hidayah, E. N.

2018-01-01

Natural organic matter (NOM) is heterogenous mixture of organic compounds that enter the water from various decomposition and metabolic reactions, including animal, plant, domestic and industrial wastes. NOM refers to group of carbon-based compounds that are found in surface water and ground water. The aim of the study is to assess organic matter characteristics in Jagir River as drinking water source and to characterize the organic components that could be removed during coagulation. Coagulation is the common water treatment process can be used to remove NOM with FeCl3 coagulant in various dosage. NOM surrogates, including total organic carbon (TOC), ultraviolet absorbance at 254 nm (UV254) and specific UV absorbance (SUVA) were chosen to assess the organic removal. Results of jar test experiments showed that NOM can be removed about 40% of NOM surrogates with 200 mg/L FeCl3. About 60% removal of total organic fraction, which is mainly humic substances, as detected by size exclusion chromatography (SEC).

Effect of different drying techniques on bioactive components, fatty acid composition, and volatile profile of robusta coffee beans.

PubMed

Dong, Wenjiang; Hu, Rongsuo; Chu, Zhong; Zhao, Jianping; Tan, Lehe

2017-11-01

This study investigated the effect of different drying techniques, namely, room-temperature drying (RTD), solar drying (SD), heat-pump drying (HPD), hot-air drying (HAD), and freeze drying (FD), on bioactive components, fatty acid composition, and the volatile compound profile of robusta coffee beans. The data showed that FD was an effective method to preserve fat, organic acids, and monounsaturated fatty acids. In contrast, HAD was ideal for retaining polyunsaturated fatty acids and amino acids. Sixty-two volatile compounds were identified in the differently dried coffee beans, representing 90% of the volatile compounds. HPD of the coffee beans produced the largest number of volatiles, whereas FD resulted in the highest volatile content. A principal component analysis demonstrated a close relationship between the HPD, SD, and RTD methods whereas the FD and HAD methods were significantly different. Overall, the results provide a basis for potential application to other similar thermal sensitive materials. Copyright © 2017 Elsevier Ltd. All rights reserved.

Contribution of microorganisms to non-extractable residue formation from biodegradable organic contaminants in soil

NASA Astrophysics Data System (ADS)

Nowak, K. M.; Girardi, C.; Miltner, A.; Schäffer, A.; Kästner, M.

2012-04-01

Biodegradation of organic contaminants in soil is actually understood as their transformation into various primary metabolites, microbial biomass, mineralisation products and non-extractable residues (NER). NER are generally considered to be composed of parent compounds or primary metabolites with hazardous potential. Up to date, however, their chemical composition remains still unclear. Studies on NER formation are limited to quantitative analyses in soils or to simple humic acids-contaminant systems. However, in the case of biodegradable organic compounds, NER may also contain microbial biomass components, e.g. fatty acids (FA) and amino acids (AA). After cell death, these biomolecules are incorporated into soil organic matter (SOM) and stabilised, ultimately forming biogenic residues which are not any more extractable. We investigated the incorporation of the 13C-label into FA and AA and their fate during biodegradation experiments in soil with isotope-labelled 2,4-dichlorophenoxyacetic acid (13C6-2,4-D) and ibuprofen (13C6-ibu) as model organic contaminants. Our study proved for the first time that nearly all NER formed from 13C6-2,4-D and 13C6-ibu in soil derived from harmless microbial biomass components stabilised in SOM. 13C-FA and 13C-AA contents in the living microbial biomass fraction decreased over time and these components were continuously incorporated into the non-living SOM pool in biotic experiments with 13C6-2,4-D and 13C6-ibu. The 13C-AA in the non-living SOM were surprisingly stable from day 32 (13C6-2,4-D) and 58 (13C6-ibu) until the end of incubation. We also studied the transformation of 13C6-2,4-D and 13C6-ibu into NER in the abiotic soil experiments. In these experiments, the total NER contents were much lower than in the corresponding biotic experiments. The absence of labelled biomolecules in the NER fraction in abiotic soils demonstrated that they consist of the potentially hazardous parent compounds and / or their metabolites. Biogenic residue formation is relevant during biodegradation of organic contaminants, whereas abiotic NER are formed from the non-biodegraded residual contaminants. Abiotic NER and biogenic residue formation are competitive processes and do not occur in a similar extent. In the biotic treatment, the rapid mineralisation of an organic compound reduces the extent of abiotic NER formation via physico-chemical interactions between a parent compound and / or its primary metabolites with SOM. Therefore, in order to properly assess the potential risks of a target contaminant in soil to humans and the environment, it is necessary to distinguish between abiotic NER and biogenic residue formation in the mass balances of contaminants.

40 CFR 59.105 - Reporting requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Volatile Organic Compound Emission Standards for Automobile Refinish Coatings § 59.105 Reporting... 180 days of the date that the regulated entity first manufactures or imports automobile refinish... States that is producing, packaging, or importing automobile refinish coatings or coating components...

40 CFR 59.105 - Reporting requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Volatile Organic Compound Emission Standards for Automobile Refinish Coatings § 59.105 Reporting... 180 days of the date that the regulated entity first manufactures or imports automobile refinish... States that is producing, packaging, or importing automobile refinish coatings or coating components...

40 CFR 59.105 - Reporting requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Volatile Organic Compound Emission Standards for Automobile Refinish Coatings § 59.105 Reporting... 180 days of the date that the regulated entity first manufactures or imports automobile refinish... States that is producing, packaging, or importing automobile refinish coatings or coating components...

PERKINELMER ELM

EPA Science Inventory

The PerkinElmer Elm (formerly the AirBase CanarIT) is a multi-sensor air quality monitoring device that measures particulate matter (PM), total volatile organic compounds (VOCs), nitrogen dioxide (NO₂), and several other atmospheric components. PM, VOCs, and NO₂

Ultrahigh Ionic Conduction in Water-Stable Close-Packed Metal-Carbonate Frameworks.

PubMed

Manna, Biplab; Desai, Aamod V; Illathvalappil, Rajith; Gupta, Kriti; Sen, Arunabha; Kurungot, Sreekumar; Ghosh, Sujit K

2017-08-21

Utilization of the robust metal-carbonate backbone in a series of water-stable, anionic frameworks has been harnessed for the function of highly efficient solid-state ion-conduction. The compact organization of hydrophilic guest ions facilitates water-assisted ion-conduction in all the compounds. The dense packing of the compounds imparts high ion-conducting ability and minimizes the possibility of fuel crossover, making this approach promising for design and development of compounds as potential components of energy devices. This work presents the first report of evaluating ion-conduction in a purely metal-carbonate framework, which exhibits high ion-conductivity on the order of 10 -2 S cm -1 along with very low activation energy, which is comparable to highly conducting well-known crystalline coordination polymers or commercialized organic polymers like Nafion.

Squalenes, phytanes and other isoprenoids as major neutral lipids of methanogenic and thermoacidophilic 'archaebacteria'

NASA Technical Reports Server (NTRS)

Tornabene, T. G.; Langworthy, T. A.; Holzer, G.; Oro, J.

1979-01-01

The neutral lipids from nine species of methanogenic bacteria (five methanobacilli, two methanococci, a methanospirillum and a methanosarcina) and two thermoacidophilic bacteria (Thermo-plasma and Sulfolobus) have been analyzed. The neutral lipids were found to comprise a wide range (C14 to C30) of polyisoprenyl hydrocarbons with varying degrees of saturation. The principal components represented the three major isoprenoid series (C20 phytanyl, C25 pentaisoprenyl, and C30 squalenyl), in contrast with the neutral lipids of extreme halophiles, which consist predominantly of C2O (phytanyl, geranylgeraniol), C30 (squalenes), C40 (carotenes) and C50 (bacterioruberins compounds), as reported by Kates (1978). These results, which indicate strong general similarities between genetically diverse organisms, support the classification of these organisms in a separate phylogenetic group. The occurrence of similar isoprenoid compounds in petroleum and ancient sediments and the fact that the methanogens, halophiles and thermoacidophiles live in conditions presumed to have prevailed in archaen times suggest that the isoprenoid compounds in petroleum compounds and sediment may have been directly synthesized by organisms of this type

Inorganic, organic and macromolecular components of fine aerosol in different areas of Europe in relation to their water solubility

NASA Astrophysics Data System (ADS)

Zappoli, S.; Andracchio, A.; Fuzzi, S.; Facchini, M. C.; Gelencsér, A.; Kiss, G.; Krivácsy, Z.; Molnár, Á.; Mészáros, E.; Hansson, H.-C.; Rosman, K.; Zebühr, Y.

A chemical mass balance of fine aerosol (<1.5 μm AED) collected at three European sites was performed with reference to the water solubility of the different aerosol classes of components. The sampling sites are characterised by different pollution conditions and aerosol loading in the air. Aspvreten is a background site in central Sweden, K-puszta is a rural site in the Great Hungarian Plain and San Pietro Capofiume is located in the polluted Po Valley, northern Italy. The average fine aerosol mass concentration was 5.9 μg m -3 at the background site Aspvreten, 24 μg m -3 at the rural K-puszta and 38 μg m -3 at the polluted site San Pietro Capofiume. However, a similarly high soluble fraction of the aerosol (65-75%) was measured at the three sites, while the percentage of water soluble organic species with respect to the total soluble mass was much higher at the background site (ca. 50%) than at the other two sites (ca. 25%). A very high fraction (over 70%) of organic compounds in the aerosol consisted of polar species. The presence of water soluble macromolecular compounds was revealed in the samples from K-puszta and San Pietro Capofiume. At both sites these species accounted for between ca. 20-50% of the water soluble organic fraction. The origin of the compounds was tentatively attributed to biomass combustion.

Dams impact carbon dynamics in U.S. rivers

NASA Astrophysics Data System (ADS)

Bhattacharya, Atreyee

2012-09-01

Dissolved organic carbon (DOC)—which leaches into freshwater systems from plants, soils, and sediments, and from other detritus present in the water itself—is the major food supplement for microorganisms and plays an important role in several environmental processes and in the global carbon cycle. In some aquatic systems such as estuaries, the optically measurable colored component of dissolved organic matter (CDOM) is often proportional to the concentration of DOC. CDOM forms when light-absorbing compounds are released into the water by decaying organic material and through photochemical degradation of certain organic compounds. Hence, CDOM reflects not just the environment and ecosystem, which is the source of the detritus, but also the processes that deliver the organic matter into aquatic systems. Human activities, such as logging, agriculture, and waste water treatment, also affect CDOM levels in aquatic systems. It is relatively easy and inexpensive to measure the CDOM content in small volumes of water.

Fractionation and characterization of organic matter in wastewater from a swine waste-retention basin

USGS Publications Warehouse

Leenheer, Jerry A.; Rostad, Colleen E.

2004-01-01

Organic matter in wastewater sampled from a swine waste-retention basin in Iowa was fractionated into 14 fractions on the basis of size (particulate, colloid, and dissolved); volatility; polarity (hydrophobic, transphilic, hydrophilic); acid, base, neutral characteristics; and precipitate or flocculates (floc) formation upon acidification. The compound-class composition of each of these fractions was determined by infrared and 13C-NMR spectral analyses. Volatile acids were the largest fraction with acetic acid being the major component of this fraction. The second most abundant fraction was fine particulate organic matter that consisted of bacterial cells that were subfractionated into extractable lipids consisting of straight chain fatty acids, peptidoglycans components of bacterial cell walls, and protein globulin components of cellular plasma. The large lipid content of the particulate fraction indicates that non-polar contaminants, such as certain pharmaceuticals added to swine feed, likely associate with the particulate fraction through partitioning interactions. Hydrocinnamic acid is a major component of the hydrophobic acid fraction, and its presence is an indication of anaerobic degradation of lignin originally present in swine feed. This is the first study to combine particulate organic matter with dissolved organic matter fractionation into a total organic matter fractionation and characterization.

Obtaining accreditation by the pharmacy compounding accreditation board, part 2: developing essential standard operating procedures.

PubMed

Cabaleiro, Joe

2007-01-01

A key component of qualifying for accreditation with the Pharmacy Compounding Accreditation Board is having a set of comprehensive standard operating procedures that are being used by the pharmacy staff. The three criteria in standard operating procedures for which the Pharmacy Compounding Accreditation Board looks are: (1)written standard operating procedures; (2)standard operating procedures that reflect what the organization actualy does; and (3) whether the written standard operating procedures are implemented. Following specified steps in the preparation of standard operating procedures will result in procedures that meet Pharmacy Compounding Accreditation Board Requirements, thereby placing pharmacies one step closer to qualifying for accreditation.

[Proteins and saponins in the lipid preparation obtained by extraction of soybean flour].

PubMed

Baukova, N A; Alekseeva, S G; Sorokoumova, G M; Selishcheva, A A; Martynova, O M; Rogozhkina, E A; Shvets, V I

2002-01-01

A complex lipid preparation was obtained by extraction of soybean flour with organic solvents. This preparation was shown to include not only phospholipids (major components), but also up to 30% saponins. These compounds were identified by TLC, HPLC, and 1H-NMR spectroscopy. Minor components of the lipid extract were represented by polypeptides associated with phospholipids via electrostatic or hydrophobic forces.

Antifungal and antibacterial activity and chemical composition of polar and non-polar extracts of Athrixia phylicoides determined using bioautography and HPLC

PubMed Central

2013-01-01

Background Athrixia phylicoides DC. (Asteraceae) is used medicinally in South Africa to treat a plethora of ailments, including heart problems, diabetes, diarrhoea, sores and infected wounds. It is also prepared in the form of a tea (hot decoction) taken as a refreshing, pleasant-tasting beverage with commercialization potential. Methods Extracts of the dried ground aerial parts were prepared using organic solvents (diethyl ether, dichloromethane/methanol, ethyl acetate and ethanol) and water. These extracts were subjected to HPLC, TLC and bioautography analysis with the aim of linking a range of peaks visualized in HPLC chromatography profiles to antibacterial and antifungal activity of the same extracts. Results HPLC revealed a group of compounds extracted by more than one solvent. Compounds identified include inositol, caffeic acid, quercetin, kaempferol, apigenin, hymenoxin and oleanolic acid. The organic extracts displayed similar TLC profiles, and bioautography indicated approximately five antibacterial compounds, but only two antifungal compounds in these extracts. Bioautography indicated that cold water extracted the least antimicrobial compounds. Conclusions Several previously unknown compounds were identified in Athrixia phylicoides extracts, and bioautography indicated a number of antibacterial and antifungal compounds. There were notable differences in chemical composition and bioactivity between the organic and aqueous extracts. Further research is necessary to fully characterize the active components of the extracts. PMID:24330447

Recent developments on ultrasound-assisted one-pot multicomponent synthesis of biologically relevant heterocycles.

PubMed

Banerjee, Bubun

2017-03-01

Heterocycles are the backbone of organic compounds. Specially, N- &O-containing heterocycles represent privileged structural subunits well distributed in naturally occurring compounds with immense biological activities. Multicomponent reactions (MCRs) are becoming valuable tool for synthesizing structurally diverse molecular entities. On the other hand, the last decade has seen a tremendous outburst in modifying chemical processes to make them sustainable for the betterment of our environment. The application of ultrasound in organic synthesis is fulfilling some of the goals of 'green and sustainable chemistry' as it has some advantages over the traditional thermal methods in terms of reaction rates, yields, purity of the products, product selectivity, etc. Therefore the synthesis of biologically relevant heterocycles using one-pot multi-component technique coupled with the application of ultrasound is one of the thrusting areas in the 21st Century among the organic chemists. The present review deals with the "up to date" developments on ultrasound assisted one-pot multi-component synthesis of biologically relevant heterocycles reported so far. Copyright © 2016 Elsevier B.V. All rights reserved.

Highly stable meteoritic organic compounds as markers of asteroidal delivery

NASA Astrophysics Data System (ADS)

Cooper, George; Horz, Friedrich; Spees, Alanna; Chang, Sherwood

2014-01-01

Multiple missions to search for water-soluble organic compounds on the surfaces of Solar System bodies are either current or planned and, if such compounds were found, it would be desirable to determine their origin(s). Asteroid or comet material is likely to have been components of all surface environments throughout Solar System history. To simulate the survival of meteoritic compounds both during impacts with planetary surfaces and under subsequent (possibly) harsh ambient conditions, we subjected known meteoritic compounds to comparatively high impact-shock pressures (>30 GPa) and/or to extremely oxidizing/corrosive acid solution. Consistent with past impact experiments, α-amino acids survived only at trace levels above ∼18 GPa. Polyaromatic hydrocarbons (PAHs) survived at levels of 4-8% at a shock pressure of 36 GPa. Lower molecular weight sulfonic and phosphonic acids (S&P) had the highest degree of impact survival of all tested compounds at higher pressures. Oxidation of compounds was done with a 3:1 mixture of HCl:HNO3, a solution that generates additional strong oxidants such as Cl2 and NOCl. Upon oxidation, keto acids and α-amino acids were the most labile compounds with proline as a significant exception. Some fraction of the other compounds, including non-α amino acids and dicarboxylic acids, were stable during 16-18 hours of oxidation. However, S&P quantitatively survived several months (at least) under the same conditions. Such results begin to build a profile of the more robust meteoritic compounds: those that may have survived, i.e., may be found in, the more hostile Solar System environments. In the search for organic compounds, one current mission, NASA's Mars Science Laboratory (MSL), will use analytical procedures similar to those of this study and those employed previously on Earth to identify many of the compounds described in this work. The current results may thus prove to be directly relevant to potential findings of MSL and other missions designed for extraterrestrial organic analysis.

INDOOR EMISSIONS FROM CONVERSION VARNISHES

EPA Science Inventory

Conversion varnishes are two-component, acid-catalyzed varnishes that are commonly used to finish cabinets. They are valued for their water- and stain-resistance, as well as their appearance. They have been found, however, to contribute to indoor emissions of organic compounds. F...

DEVELOPING A NO-VOC WOOD TOPCOAT

EPA Science Inventory

The paper reports an evaluation of a new low-VOC (volatile organic compound) wood coating technology, its performance characteristics, and its application and emissions testing. The low-VOC wood coating selected for the project was a two-component, water-based epoxy coating. Poly...

Volatility of source apportioned wintertime organic aerosol in the city of Athens

NASA Astrophysics Data System (ADS)

Louvaris, Evangelos E.; Florou, Kalliopi; Karnezi, Eleni; Papanastasiou, Dimitrios K.; Gkatzelis, Georgios I.; Pandis, Spyros N.

2017-06-01

The volatility distribution of ambient organic aerosol (OA) and its components was measured during the winter of 2013 in the city of Athens combining a thermodenuder (TD) and a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). Positive Matrix Factorization (PMF) analysis of both the ambient and the thermodenuder AMS-spectra resulted in a four-factor solution for the OA, namely: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking OA (COA), and oxygenated OA (OOA). The thermograms of the four factors were analyzed and the corresponding volatility distributions were estimated using the volatility basis set (VBS). All four factors included compounds with a wide range of effective volatilities from 10 to less than 10-4 μg m-3 at 298 K. Almost 40% of the HOA consisted of low-volatility organic compounds (LVOCs) with the semi-volatile compounds (SVOCs) representing roughly 30%, while the remaining 30% consisted of extremely low volatility organic compounds (ELVOCs). BBOA was more volatile than the HOA factor on average, with 10% ELVOCs, 40% LVOCs, and 50% SVOCs. 10% of the COA consisted of ELVOCs, another 65% LVOCs, and 50% SVOCs. Finally, the OOA was the least volatile factor and included 40% ELVOCs, 25% LVOCs, and 35% SVOCs. Combining the volatility distributions and the O:C ratios of the various factors, we placed our results in the 2D-VBS analysis framework of Donahue et al. (2012). HOA and BBOA are in the expected region but also include an ELVOC component. COA is in similar range as HOA, but on average is half an order of magnitude more volatile. The OOA in these wintertime conditions had a moderate O:C ratio and included both semi-volatile and extremely low volatility components. The above results are sensitive to the assumed values of the effective vaporization enthalpy and the accommodation coefficient. A reduction of the accommodation coefficient by an order of magnitude or the reduction of the vaporization enthalpy by 20 kJ mol-1 results in the increase of the average volatility by half an order of magnitude.

A review of surface-water sediment fractions and their interactions with persistent manmade organic compounds

USGS Publications Warehouse

Witkowski, P.J.; Smith, J.A.; Fusillo, T.V.; Chiou, C.T.

1987-01-01

This paper reviews the suspended and surficial sediment fractions and their interactions with manmade organic compounds. The objective of this review is to isolate and describe those contaminant and sediment properties that contribute to the persistence of organic compounds in surface-water systems. Most persistent, nonionic organic contaminants, such as the chlorinated insecticides and polychlorinated biphenyls (PCBs), are characterized by low water solubilities and high octanol-water partition coefficients. Consequently, sorptive interactions are the primary transformation processes that control their environmental behavior. For nonionic organic compounds, sorption is primarily attributed to the partitioning of an organic contaminant between a water phase and an organic phase. Partitioning processes play a central role in the uptake and release of contaminants by sediment organic matter and in the bioconcentration of contaminants by aquatic organisms. Chemically isolated sediment fractions show that organic matter is the primary determinant of the sorptive capacity exhibited by sediment. Humic substances, as dissolved organic matter, contribute a number of functions to the processes cycling organic contaminants. They alter the rate of transformation of contaminants, enhance apparent water solubility, and increase the carrying capacity of the water column beyond the solubility limits of the contaminant. As a component of sediment particles, humic substances, through sorptive interactions, serve as vectors for the hydrodynamic transport of organic contaminants. The capabilities of the humic substances stem in part from their polyfunctional chemical composition and also from their ability to exist in solution as dissolved species, flocculated aggregates, surface coatings, and colloidal organomineral and organometal complexes. The transport properties of manmade organic compounds have been investigated by field studies and laboratory experiments that examine the sorption of contaminants by different sediment size fractions. Field studies indicate that organic contaminants tend to sorb more to fine-grained sediment, and this correlates significantly with sediment organic matter content. Laboratory experiments have extended the field studies to a wider spectrum of natural particulates and anthropogenic compounds. Quantitation of isotherm results allows the comparison of different sediment sorbents as well as the estimation of field partition coefficients from laboratory-measured sediment and contaminant properties. Detailed analyses made on the basis of particle-size classes show that all sediment fractions need to be considered in evaluating the fate and distribution of manmade organic compounds. This conclusion is based on observations from field studies and on the variety of natural organic sorbents that demonstrate sorptive capabilities in laboratory isotherm experiments.

Carbon, hydrogen and nitrogen isotopes in solvent-extractable organic matter from carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Becker, R. H.; Epstein, S.

1982-01-01

CCl4 and CH3OH solvent extractions were performed on the Murray, Murchison, Orgueil and Renazzo carbonaceous chondrites. Delta-D values of +300-+500% are found in the case of the CH3OH-soluble organic matter. The combined C, H and N isotope data makes it unlikely that the CH3OH-soluble components are derivable from, or simply related to, the insoluble organic polymer found in the same meteorites. A relation between the event that formed hydrous minerals in CI1 and CM2 meteorites and the introduction of water- and methanol-soluble organic compounds is suggested. Organic matter soluble in CCl4 has no N, and delta-C-13 values are lower than for CH3OH-soluble phases. It is concluded that there either are large isotopic fractionations for carbon and hydrogen between different soluble organic phases, or the less polar components are partially of terrestrial origin.

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

NASA Technical Reports Server (NTRS)

Huang, Chen-Kuo (Inventor); Smart, Marshall C. (Inventor); Surampudi, Subbarao (Inventor); Bugga, Ratnakumar V. (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

Identification of (E,E)-2,4-undecadienal from coriander (Coriandrum sativum L.) as a highly effective deodorant compound against the offensive odor of porcine large intestine.

PubMed

Ikeura, Hiromi; Kohara, Kaori; Li, Xin-Xian; Kobayashi, Fumiyuki; Hayata, Yasuyoshi

2010-10-27

The leaves of coriander ( Coriandrum sativum L.) exhibited a strong deodorizing effect against porcine internal organs (large intestine). The effective deodorizing compounds of coriander were identified by separating the volatile component of coriander, testing the effectiveness of each fraction against the offensive odor of porcine large intestine, and then identifying the compounds by GC-MS. The volatile component of coriander was first separated into six fractions (A-F) by preparative gas chromatography, and the deodorizing activity of each of these fractions against the offensive odor was measured. Fraction D, which showed the strongest deodorizing effect, was then separated into 12 subfractions by preparative GC. The deodorant activity of each subfraction was evaluated, and the deodorant compounds were identified by GC-MS. It was discovered that (E,E)-2,4-undecadienal was the most effective deodorizing compound. The deodorizing activity of (E,E)-2,4-undecadienal on the porcine large intestine increased as with concentration, reaching almost complete deodorizing ability at 10 ppb.

Data-driven signal-resolving approaches of infrared spectra to explore the macroscopic and microscopic spatial distribution of organic and inorganic compounds in plant.

PubMed

Chen, Jian-bo; Sun, Su-qin; Zhou, Qun

2015-07-01

The nondestructive and label-free infrared (IR) spectroscopy is a direct tool to characterize the spatial distribution of organic and inorganic compounds in plant. Since plant samples are usually complex mixtures, signal-resolving methods are necessary to find the spectral features of compounds of interest in the signal-overlapped IR spectra. In this research, two approaches using existing data-driven signal-resolving methods are proposed to interpret the IR spectra of plant samples. If the number of spectra is small, "tri-step identification" can enhance the spectral resolution to separate and identify the overlapped bands. First, the envelope bands of the original spectrum are interpreted according to the spectra-structure correlations. Then the spectrum is differentiated to resolve the underlying peaks in each envelope band. Finally, two-dimensional correlation spectroscopy is used to enhance the spectral resolution further. For a large number of spectra, "tri-step decomposition" can resolve the spectra by multivariate methods to obtain the structural and semi-quantitative information about the chemical components. Principal component analysis is used first to explore the existing signal types without any prior knowledge. Then the spectra are decomposed by self-modeling curve resolution methods to estimate the spectra and contents of significant chemical components. At last, targeted methods such as partial least squares target can explore the content profiles of specific components sensitively. As an example, the macroscopic and microscopic distribution of eugenol and calcium oxalate in the bud of clove is studied.

Evaluation of solvent effect on the extraction of phenolic compounds and antioxidant capacities from the berries: application of principal component analysis.

PubMed

Boeing, Joana Schuelter; Barizão, Erica Oliveira; E Silva, Beatriz Costa; Montanher, Paula Fernandes; de Cinque Almeida, Vitor; Visentainer, Jesuí Vergilio

2014-01-01

This study evaluated the effect of the solvent on the extraction of antioxidant compounds from black mulberry (Morus nigra), blackberry (Rubus ulmifolius) and strawberry (Fragaria x ananassa). Different extracts of each berry were evaluated from the determination of total phenolic content, anthocyanin content and antioxidant capacity, and data were applied to the principal component analysis (PCA) to gain an overview of the effect of the solvent in extraction method. For all the berries analyzed, acetone/water (70/30, v/v) solvent mixture was more efficient solvent in the extracting of phenolic compounds, and methanol/water/acetic acid (70/29.5/0.5, v/v/v) showed the best values for anthocyanin content. Mixtures of ethanol/water (50/50, v/v), acetone water/acetic acid (70/29.5/0.5, v/v/v) and acetone/water (50/50, v/v) presented the highest antioxidant capacities for black mulberries, blackberries and strawberries, respectively. Antioxidants extractions are extremely affected by the solvent combination used. In addition, the obtained extracts with the organic solvent-water mixtures were distinguished from the extracts obtained with pure organic solvents, through the PCA analysis.

Refractory Organic Compounds in Enceladus' Ice Grains and Hydrothermal Activity

NASA Astrophysics Data System (ADS)

Postberg, F.; Khawaja, N.; Hsu, H. W.; Sekine, Y.; Shibuya, T.

2015-12-01

Cassini's Cosmic Dust Analyzer (CDA) generates time-of-flight mass spectra of individual grains impinging on the instruments target-plate. Following the analysis of salt rich ice grains emitted by Enceladus that indicated a salt-water ocean in contact with the moon's rocky core [1,2] a recent CDA analysis of nano-phase silica particles pointed at hydrothermal activity at the moon's rock/water interface [3]. The results imply temperatures above 80 - 90°C and alkaline pH values around 10 reminiscent of alkaline hydrothermal vents on Earth like the Lost City Hydrothermal Field. In this context the compositional analysis of organic components in CDA mass spectra of the ejected ice grains is of particular relevance. A multitude of volatile organic species has already been identified in the gas component of the plume [4]. As expected, we find more complex organic molecules in ice grains than in the gas indicating aromatic species, amines, and carbonyl group species. The composition of organic-bearing ice grains displays a great diversity indicating a variety of different organic species in varying concentrations. Recent spatially resolved CDA in situ measurements inside Enceladus' plume indicate that these organic compounds are especially frequent in 'young' ice grains that have just been ejected by high velocity jets. We investigate the implications of our findings with respect to ice grain formation at the water surface and inside the icy vents. We constrain the generation of organic compounds at the rock/water interface in the light of hydrothermal activity and the potential for the formation of life precursor molecules in Enceladus' ocean. Ref:[1] Postberg et al., Nature 459, 1098-1101 (2009). [2] Postberg et al., Nature 474, 620-622 (2011). [3]. Hsu, Postberg, Sekine et al., Nature, 519, 207-210 (2015). [4] Waite et al., Nature 460, 487-490 (2009).

Mediated electrochemical oxidation of organic wastes using a Co (III) mediator in a nitric acid based system

DOEpatents

Balazs, G. Bryan; Chiba, Zoher; Lewis, Patricia R.; Nelson, Norvell; Steward, G. Anthony

1999-01-01

An electrochemical cell with a Co(III) mediator and nitric acid electrolyte provides efficient destruction of organic and mixed wastes. The organic waste is concentrated in the anolyte reservoir, where the mediator oxidizes the organics and insoluble transuranic compounds and is regenerated at the anode until the organics are converted to CO.sub.2. The nitric acid is an excellent oxidant that facilitates the destruction of the organic components. The anode is not readily attacked by the nitric acid solution, thus the cell can be used for extended continual operation without electrode replacement.

Historic records of organic compounds from a high Alpine glacier: influences of biomass burning, anthropogenic emissions, and dust transport

NASA Astrophysics Data System (ADS)

Müller-Tautges, C.; Eichler, A.; Schwikowski, M.; Pezzatti, G. B.; Conedera, M.; Hoffmann, T.

2016-01-01

Historic records of α-dicarbonyls (glyoxal, methylglyoxal), carboxylic acids (C6-C12 dicarboxylic acids, pinic acid, p-hydroxybenzoic acid, phthalic acid, 4-methylphthalic acid), and ions (oxalate, formate, calcium) were determined with annual resolution in an ice core from Grenzgletscher in the southern Swiss Alps, covering the time period from 1942 to 1993. Chemical analysis of the organic compounds was conducted using ultra-high-performance liquid chromatography (UHPLC) coupled to electrospray ionization high-resolution mass spectrometry (ESI-HRMS) for dicarbonyls and long-chain carboxylic acids and ion chromatography for short-chain carboxylates. Long-term records of the carboxylic acids and dicarbonyls, as well as their source apportionment, are reported for western Europe. This is the first study comprising long-term trends of dicarbonyls and long-chain dicarboxylic acids (C6-C12) in Alpine precipitation. Source assignment of the organic species present in the ice core was performed using principal component analysis. Our results suggest biomass burning, anthropogenic emissions, and transport of mineral dust to be the main parameters influencing the concentration of organic compounds. Ice core records of several highly correlated compounds (e.g., p-hydroxybenzoic acid, pinic acid, pimelic, and suberic acids) can be related to the forest fire history in southern Switzerland. P-hydroxybenzoic acid was found to be the best organic fire tracer in the study area, revealing the highest correlation with the burned area from fires. Historical records of methylglyoxal, phthalic acid, and dicarboxylic acids adipic acid, sebacic acid, and dodecanedioic acid are comparable with that of anthropogenic emissions of volatile organic compounds (VOCs). The small organic acids, oxalic acid and formic acid, are both highly correlated with calcium, suggesting their records to be affected by changing mineral dust transport to the drilling site.

Partially oxidised organic components in urban aerosol using GCXGC-TOF/MS

NASA Astrophysics Data System (ADS)

Hamilton, J. F.; Webb, P. J.; Lewis, A. C.; Hopkins, J. R.; Smith, S.; Davy, P.

2004-08-01

Partially oxidised organic compounds associated with PM2.5 aerosol collected in London, England, have been analysed using direct thermal desorption coupled to comprehensive gas chromatography-time of flight mass spectrometry (GCXGC-TOF/MS). Over 10000 individual organic components were isolated from around 10µg of aerosol material in a single procedure and with no sample pre-treatment. Chemical functionalities observed using this analytical technique ranged from alkanes to poly-oxygenated species. The chemical band structures commonly used in GCXGC for group type identifications overlap for this sample type, and have required mass spectrometry as an additional level of instrument dimensionality. An investigation of oxygenated volatile organic compounds (o-VOC) contained within urban aerosol has been performed and in a typical sample around 130 o-VOCs were identified based on retention behaviour and spectral match. In excess of 100 other oxygenated species were also observed but lack of mass spectral library or pure components prevents positive identification. Many of the carbonyl species observed could be mechanistically linked to gas phase aromatic hydrocarbon oxidation and there is good agreement in terms of speciation between the urban samples analysed here and those degradation products observed in smog chamber experiments of aromatic oxidation. The presence of partially oxidised species such as linear chain aldehydes and ketones and cyclic products such as furanones suggests that species generated early in the oxidative process may undergo gas to particle partitioning despite their relatively high volatility.

Partially oxidised organic components in urban aerosol using GCXGC-TOF/MS

NASA Astrophysics Data System (ADS)

Hamilton, J.; Webb, P.; Lewis, A.; Hopkins, J.; Smith, S.; Davy, P.

2004-03-01

Partially oxidised organic compounds associated with PM2.5 aerosol collected in London, England, have been analysed using direct thermal desorption coupled to comprehensive gas chromatography-time of flight mass spectrometry (GCXGC-OF/MS). Over 10 000 individual organic components were isolated from around 10 μg of aerosol material in a single procedure and with no sample pre-treatment. Chemical functionalities observed using this analytical technique ranged from alkanes to poly-oxygenated species. The chemical band structures commonly used in GCXGC for group type identifications overlap for this sample type, and have required mass spectrometry as an additional level of instrument dimensionality. An investigation of oxygenated volatile organic compounds (o-VOC) contained within urban aerosol has been performed and in a typical sample around 130 o-VOCs were identified based on retention behaviour and spectral match. In excess of 100 other oxygenated species were also observed but lack of mass spectral library or pure components prevents positive identification. Many of the carbonyl species observed could be mechanistically linked to gas phase aromatic hydrocarbon oxidation and there is good agreement in terms of speciation between the urban samples analysed here and those degradation products observed in smog chamber experiments of aromatic oxidation. The presence of partially oxidised species such as linear chain aldehydes and ketones and cyclic products such as furanones suggests that species generated relatively early in the oxidative process may undergo gas to particle partitioning despite their relatively high volatility.

Water-quality assessment of the Rio Grande Valley, Colorado, New Mexico and Texas; organic compounds and trace elements in bed sediment and fish tissue, 1992-93

USGS Publications Warehouse

Carter, L.F.; Anderholm, S.K.

1997-01-01

The occurrence and distribution of contaminants in aquatic systems are major components of the National Water-Quality Assessment (NAWQA) Program. Bed-sediment samples were collected at 18 sites in the Rio Grande Valley study unit between September 1992 and March 1993 to characterize the geographic distribution of organic compounds, including chlorinated insecticides, polychlorinated biphenyls (PCB's), and other chlorinated hydrocarbons, and also trace elements. Two-millimeter-size- fraction sediment was analyzed for organic compounds and less than 63-micron-size-fraction sediment was analyzed for trace elements. Concentrations of p,p'-DDE were detected in 33 percent of the bed-sediment samples. With the exception of DDT-related compounds, no other organochlorine insecticides or polychlorinated biphenyls were detected in samples of bed sediment. Whole-body fish samples were collected at 11 of the bed- sediment sites and analyzed for organic compounds. Organic compounds were reported more frequently in samples of fish, and more types of organic compounds were found in whole-body fish samples than in bed-sediment samples. Concentrations of p,p'-DDE were detected in 91 percent of whole-body fish samples. Polychlorinated biphenyls, cis-chlordane, trans-chlordane, trans- nonachlor, and hexachlorobenzene were other organic compounds detected in whole-body samples of fish from at least one site. Because of the extent of mineralized areas in the Rio Grande Basin arsenic, cadmium, copper, lead, mercury, selenium, and zinc concentrations in bed-sediment samples could represent natural conditions at most sites. However, a combination of natural conditions and human activities appears to be associated with elevated trace-element concentrations in the bed-sediment sample from the site Rio Grande near Creede, Colorado, because this sample exceeded the background trace-element concentrations calculated for this study. Fish-liver samples were collected at 12 of the bed-sediment sites and analyzed for trace elements. Certain trace elements were detected at higher concentrations in fish-liver samples than in bed-sediment samples from the same site. Both bed-sediment and fish-tissue samples are necessary for a complete environmental assessment of the occurrence and distribution of trace elements.

Subcritical water extraction of organic matter from sedimentary rocks.

PubMed

Luong, Duy; Sephton, Mark A; Watson, Jonathan S

2015-06-16

Subcritical water extraction of organic matter containing sedimentary rocks at 300°C and 1500 psi produces extracts comparable to conventional solvent extraction. Subcritical water extraction of previously solvent extracted samples confirms that high molecular weight organic matter (kerogen) degradation is not occurring and that only low molecular weight organic matter (free compounds) are being accessed in analogy to solvent extraction procedures. The sedimentary rocks chosen for extraction span the classic geochemical organic matter types. A type I organic matter-containing sedimentary rock produces n-alkanes and isoprenoidal hydrocarbons at 300°C and 1500 psi that indicate an algal source for the organic matter. Extraction of a rock containing type II organic matter at the same temperature and pressure produces aliphatic hydrocarbons but also aromatic compounds reflecting the increased contributions from terrestrial organic matter in this sample. A type III organic matter-containing sample produces a range of non-polar and polar compounds including polycyclic aromatic hydrocarbons and oxygenated aromatic compounds at 300°C and 1500 psi reflecting a dominantly terrestrial origin for the organic materials. Although extraction at 300°C and 1500 psi produces extracts that are comparable to solvent extraction, lower temperature steps display differences related to organic solubility. The type I organic matter produces no products below 300°C and 1500 psi, reflecting its dominantly aliphatic character, while type II and type III organic matter contribute some polar components to the lower temperature steps, reflecting the chemical heterogeneity of their organic inventory. The separation of polar and non-polar organic compounds by using different temperatures provides the potential for selective extraction that may obviate the need for subsequent preparative chromatography steps. Our results indicate that subcritical water extraction can act as a suitable replacement for conventional solvent extraction of sedimentary rocks, but can also be used for any organic matter containing mineral matrix, including soils and recent sediments, and has the added benefit of tailored extraction for analytes of specific polarities. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Heterogeneous Oxidation of Laboratory-generated Mixed Composition and Biomass Burning Particles

NASA Astrophysics Data System (ADS)

Lim, C. Y.; Sugrue, R. A.; Hagan, D. H.; Cappa, C. D.; Kroll, J. H.; Browne, E. C.

2016-12-01

Heterogeneous oxidation of organic aerosol (OA) can significantly transform the chemical and physical properties of particulate matter in the atmosphere, leading to changes to the chemical composition of OA and potential volatilization of organic compounds. It has become increasingly apparent that the heterogeneous oxidation kinetics of OA depend on the phase and morphology of the particles. However, most laboratory experiments to date have been performed on single-component, purely organic precursors, which may exhibit fundamentally different behavior than more complex particles in the atmosphere. Here we present laboratory studies of the heterogeneous oxidation of two more complex chemical systems: thin, organic coatings on inorganic seed particles and biomass burning OA. In the first system, squalane (C30H62), a model compound for reduced OA, is coated onto dry ammonium sulfate particles at various thicknesses (10-20 nm) and exposed to hydroxyl radical (OH) in a flow tube reactor. In the second, we use a semi-batch reactor to study the heterogeneous OH-initiated oxidation of biomass burning particles as a part of the 2016 FIREX campaign in Missoula, MT. The resulting changes in chemical composition are monitored with an Aerodyne High Resolution Time-of-flight Aerosol Mass Spectrometer (AMS) and a soot-particle AMS for the non-refractory and refractory systems, respectively. We show that the heterogeneous oxidation kinetics of these multicomponent particles are substantially different than that of the single-component particles. The oxidation of organic coatings is rapid, undergoing dramatic changes to carbon oxidation state and losing a significant amount of organic mass after relatively low OH exposures (equivalent to several days of atmospheric processing). In the case of biomass burning particles, the kinetics are complex, with different components (inferred by aerosol mass spectrometry) undergoing oxidation at different rates.

GREENER CHEMICAL SYNTHETIC APPROACHES TO HETEROCYCLES, NOBLE NANOMETALS, AND NANOCOMPOSITES

EPA Science Inventory

An efficient and sustainable approach to rapid organic synthesis using ‘greener’ conditions, especially in the context of multi-component condensation reactions that are amenable to building libraries of compounds, is described. The use of solvent-free mechanochemical mixing, or ...

The Changes in Color, Soluble Sugars, Organic Acids, Anthocyanins and Aroma Components in "Starkrimson" during the Ripening Period in China.

PubMed

Liu, Yulian; Chen, Nianlai; Ma, Zonghuan; Che, Fei; Mao, Juan; Chen, Baihong

2016-06-22

"Starkrimson" is a traditional apple cultivar that was developed a long time ago and was widely cultivated in the arid region of the northern Wei River of China. However, little information regarding the quality characteristics of "Starkrimson" fruit has been reported in this area. To elucidate these characteristics, the color, soluble sugars, organic acids, anthocyanins and aroma components were measured during the ripening period through the use of high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). The results indicated that the changes in anthocyanin contents took place later than the changes in the Commission International Eclairage (CIE) parameters. Meanwhile, cyanidin 3-galactoside (cy3-gal), fructose, sucrose, glucose and malic acid were the primary organic compounds, and 1-butanol-2-methyl-acetate, 2-hexenal and 1-hexanol were the most abundant aroma components in the skin. Furthermore, rapidly changing soluble sugars and organic acid synchronization took place in the early ripening period, while rapidly changing aroma components occurred later, on the basis of fresh weight. This result suggested that the production of aroma components might be a useful index of apple maturity.

X-ray diffraction study of the molecular propolis films deposited from an alcohol solution onto the cleavage surfaces of layered V2VI3 compounds

NASA Astrophysics Data System (ADS)

Drapak, S. I.; Gavrylyuk, S. V.; Kaminskii, V. M.; Kovalyuk, Z. D.

2008-09-01

The structures of the molecular propolis films deposited from an alcohol solution on the (0001) cleavage surface of layered bismuth selenide and telluride are studied by X-ray diffraction. Despite the chemical interaction between the semiconductor substrates and the organic-substance components, the molecular structural ordering of the propolis films is shown to be identical to that in the films of this substance on the surface of amorphous glass substrates. The chemical and deformation interaction between the organic substance and the layered V2VI3 compounds is found to result in the formation of an organic-inorganic sandwich nanostructure at a distance of ˜0.3 μm from the layered crystal-propolis film interface.

Organics in water contamination analyzer, phase 1

NASA Technical Reports Server (NTRS)

1986-01-01

The requirements which would result in identifying the components of an automatic analytical system for the analysis of specific organic compounds in the space station potable water supply are defined. The gas chromatographic system for such an analysis is limited to commercially available off-the-shelf hardware and includes the sample inlet, an ionization detector, capillary columns as well as computerized compound identification. The sampling system will be a special variation of the purge and trap Tenax mode using six-port valves and a 500 microliter water sample. Capillary columns used for the separating of contaminants will be bonded phase fused silica with a silicone stationary phase. Two detectors can be used: photoionization and far ultraviolet, since they are sensitive and compatible with capillary columns. A computer system evaluation and program with the principle of compound identification based on the retention index is presented.

Chemical compositions and sources of organic matter in fine particles of soils and sands from the vicinity of Kuwait city.

PubMed

Rushdi, Ahmed I; Al-Zarban, Sheikha; Simoneit, Bernd R T

2006-09-01

Fine particles in the atmosphere from soil and sand resuspension contain a variety of organic compounds from natural biogenic and anthropogenic matter. Soil and sand samples from various sites near Kuwait city were collected, sieved to retain the fine particles, and extracted with a mixture of dichloromethane and methanol. The extracts were derivatized and analyzed by gas chromatography-mass spectrometry in order to characterize the chemical compositions and sources of the organic components. The major inputs of organic compounds were from both natural biogenic and anthropogenic sources in these samples. Vegetation was the major natural source of organic compounds and included n-alkanols, n-alkanoic acids, n-alkanes, sterols and triterpenoids. Saccharides had high concentrations (31-43%) in the sand dune and seafront samples, indicating sources from decomposed vegation materials and/or the presence of viable microbiota such as bacteria and fungi. Vehicular emission products, leakage of lubricating oils, discarded plastics and emissions from cooking operations were the major anthropogenic inputs in the samples from the urban areas. This input was mainly UCM, n-alkanes, hopanes, plasticizers and cholesterol, respectively.

Validation of Direct Analysis Real Time source/Time-of-Flight Mass Spectrometry for organophosphate quantitation on wafer surface.

PubMed

Hayeck, Nathalie; Ravier, Sylvain; Gemayel, Rachel; Gligorovski, Sasho; Poulet, Irène; Maalouly, Jacqueline; Wortham, Henri

2015-11-01

Microelectronic wafers are exposed to airborne molecular contamination (AMC) during the fabrication process of microelectronic components. The organophosphate compounds belonging to the dopant group are one of the most harmful groups. Once adsorbed on the wafer surface these compounds hardly desorb and could diffuse in the bulk of the wafer and invert the wafer from p-type to n-type. The presence of these compounds on wafer surface could have electrical effect on the microelectronic components. For these reasons, it is of importance to control the amount of these compounds on the surface of the wafer. As a result, a fast quantitative and qualitative analytical method, nondestructive for the wafers, is needed to be able to adjust the process and avoid the loss of an important quantity of processed wafers due to the contamination by organophosphate compounds. Here we developed and validated an analytical method for the determination of organic compounds adsorbed on the surface of microelectronic wafers using the Direct Analysis in Real Time-Time of Flight-Mass Spectrometry (DART-ToF-MS) system. Specifically, the developed methodology concerns the organophosphate group. Copyright © 2015 Elsevier B.V. All rights reserved.

Recent Discoveries and Future Challenges in Atmospheric Organic Chemistry.

PubMed

Glasius, Marianne; Goldstein, Allen H

2016-03-15

Earth's atmosphere contains a multitude of organic compounds, which differ by orders of magnitude regarding fundamental properties such as volatility, reactivity, and propensity to form cloud droplets, affecting their impact on global climate and human health. Despite recent major research efforts and advances, there are still substantial gaps in understanding of atmospheric organic chemistry, hampering efforts to understand, model, and mitigate environmental problems such as aerosol formation in both polluted urban and more pristine regions. The analytical toolbox available for chemists to study atmospheric organic components has expanded considerably during the past decade, opening new windows into speciation, time resolution and detection of reactive and semivolatile compounds at low concentrations. This has provided unprecedented opportunities, but also unveiled new scientific challenges. Specific groundbreaking examples include the role of epoxides in aerosol formation especially from isoprene, the importance of highly oxidized, reactive organics in air-surface processes (whether atmosphere-biosphere exchange or aerosols), as well as the extent of interactions of anthropogenic and biogenic emissions and the resulting impact on atmospheric organic chemistry.

Relation between the location of elements in the periodic table and various organ-uptake rates.

PubMed

Ando, A; Ando, I; Hiraki, T; Hisada, K

1989-01-01

Fifty four elements and 65 radioactive compounds were examined to determine the organ uptake rates for rats 3, 24 and 48 h after i.v. injection of these compounds. They were prepared as carrier free nuclides, or containing a small amount of stable nuclide. Generally speaking, behaviors of K, Rb, Cs and Tl in all the organs were very similar to one another, but they differed from that of Na. Bivalent hard acids were avidly taken up into bone; therefore, uptake rates in soft tissues were very small. Hard acids of tri-, quadri- and pentavalence which were taken up into the soft tissue organs decreased more slowly from these organs than other ions. Soft acids such as Hg2+ were bound very firmly to the component in the kidney. Anions (with few exceptions), GeCl4 and SbCl3 were rapidly excreted in urine, so that the uptake rates in organs were low.

Microbial and long-range terrestrial contributions of organic matter to Antarctica

NASA Astrophysics Data System (ADS)

Antony, R.; Grannas, A. M.; Priest, A. S.; Sleighter, R. L.; Meloth, T.; Hatcher, P.

2012-12-01

Composition and cycling of dissolved organic matter in glacial systems is important because of its great significance to global carbon dynamics, snow photochemistry, and air-snow exchange processes. But, due to the trace nature of specific organic components in Polar ice sheets, detecting and studying these species in molecular level detail has been an analytical challenge. Electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) enabled the elucidation of molecular level details of natural organic matter in snow samples collected along a coast to inland transect from the Princesses Elizabeth Land, East Antarctica. Thousands of distinct molecular species comprising of different compound classes were identified providing clues to the nature and sources of organic carbon in Antarctic snow. The major biochemical classes of compounds detected were lignins, tannins, carbohydrates, proteins, amino sugars, lipids, unsaturated hydrocarbons and condensed aromatics. Specifically, lignin molecules comprising up to 50% and compounds derived from algal and microbial biomass comprising up to 45% of the total assigned formulas dominated the organic carbon pool. The identification of a variety of lignin compounds demonstrates substantial input of vascular plant-derived materials to the identified molecular species, presumably from long range atmospheric transport and deposition. The detection of proteins, lipids and amino sugars suggests that a large proportion of the identified supraglacial organic matter likely originates from in situ microbial activity. This corroborates well with the presence of significant numbers of bacteria, picoplankton and microalgae in these samples. These results suggest that organic matter in the supraglacial environments have both a microbial and terrestrial provenance.

Thermochemolysis and the Search for Organic Material on Mars Onboard the MOMA Experiment

NASA Astrophysics Data System (ADS)

Morisson, Marietta; Buch, Arnaud; Szopa, Cyril; Glavin, Daniel; Freissinet, Carolinette; Pinnick, Veronica; Goetz, Walter; Stambouli, Moncef; Belmahdi, Imene; Coll, Patrice; Stalport, Fabien; Grand, Noël; Brinckerhoff, William; Goesmann, Fred; Raulin, François; Mahaffy, Paul

2016-04-01

Following the Sample Analysis at Mars (SAM) experiment onboard the Curiosity rover, the Mars Organic Molecule Analyzer (MOMA) experiment onboard the future ExoMars 2018 mission will continue to investigate the organic composition of the martian subsurface. MOMA will have the advantage of extracting the sample from as deep as 2 meters below the martian surface where the deleterious effects of radiation and oxidation on organic matter are minimized. To analyse the wide range of organic compounds (volatile and non-volatile compounds) potentially present in the martian soil, MOMA includes two operational modes: UV laser desorption / ionization ion trap mass spectrometry (LDI-ITMS) and pyrolysis gas chromatography ion trap mass spectrometry (pyr-GC-ITMS). In order to analyse refractory organic compounds and chirality, samples which undergo GC-ITMS analysis may be derivatized beforhands, consisting in the reaction of the sample components with specific chemical reagents (MTBSTFA [1], DMF-DMA [2] or TMAH [3]). To prove the feasibility of the derivatization within the MOMA conditions we have adapated our laboratory procedure for the space conditions (temperature, time, pressure and size). Goal is optimize our detection limits and increase the range of the organic compounds that MOMA will be able to detect. Results of this study, show that Thermochemolysis is one of the most promising technique onboard MOMA to detect organic material. References : [1] Buch, A. et al. (2009) J Chrom. A, 43, 143-151. [2] Freissinet, C. et al. (2013) J Chrom. A, 1306, 731-740. [3] Geffroy-Rodier, C. et al. (2009) JAAP, 85, 454-459.

Heme compounds as iron sources for nonpathogenic Rhizobium bacteria.

PubMed Central

Noya, F; Arias, A; Fabiano, E

1997-01-01

Many animal-pathogenic bacteria can use heme compounds as iron sources. Like these microorganisms, rhizobium strains interact with host organisms where heme compounds are available. Results presented in this paper indicate that the use of hemoglobin as an iron source is not restricted to animal-pathogenic microorganisms. We also demonstrate that heme, hemoglobin, and leghemoglobin can act as iron sources under iron-depleted conditions for Rhizobium meliloti 242. Analysis of iron acquisition mutant strains indicates that siderophore-, heme-, hemoglobin-, and leghemoglobin-mediated iron transport systems expressed by R. meliloti 242 share at least one component. PMID:9139934

Heme compounds as iron sources for nonpathogenic Rhizobium bacteria.

PubMed

Noya, F; Arias, A; Fabiano, E

1997-05-01

Many animal-pathogenic bacteria can use heme compounds as iron sources. Like these microorganisms, rhizobium strains interact with host organisms where heme compounds are available. Results presented in this paper indicate that the use of hemoglobin as an iron source is not restricted to animal-pathogenic microorganisms. We also demonstrate that heme, hemoglobin, and leghemoglobin can act as iron sources under iron-depleted conditions for Rhizobium meliloti 242. Analysis of iron acquisition mutant strains indicates that siderophore-, heme-, hemoglobin-, and leghemoglobin-mediated iron transport systems expressed by R. meliloti 242 share at least one component.

Molecular Insights into Arctic Soil Organic Matter Degradation under Warming

DOE PAGES

Chen, Hongmei; Yang, Ziming; Chu, Rosalie K.; ...

2018-03-23

Molecular composition of the Arctic soil organic carbon (SOC) and its susceptibility to microbial degradation are uncertain due to heterogeneity and unknown SOC compositions. By using ultrahigh-resolution mass spectrometry, we determined the susceptibility and compositional changes of extractable dissolved organic matter (EDOM) in an anoxic warming incubation experiment (up to 122 days) with a tundra soil from Alaska (United States). EDOM was extracted with 10 mM NH 4HCO 3 from both the organic- and mineral-layer soils during incubation at both -2 and 8°C. Based on their O:C and H:C ratios, EDOM molecular formulas were qualitatively grouped into nine biochemical classesmore » of compounds, among which lignin-like compounds dominated both the organic and the mineral soils and were the most stable, whereas amino sugars, peptides, and carbohydrate-like compounds were the most biologically labile. These results corresponded with shifts in EDOM elemental composition in which the ratios of O:C and N:C decreased, while the average C content in EDOM, molecular mass, and aromaticity increased after 122 days of incubation. This research demonstrates that certain EDOM components, such as amino sugars, peptides, and carbohydrate-like compounds, are disproportionately more susceptible to microbial degradation than others in the soil, and these results should be considered in SOC degradation models to improve predictions of Arctic climate feedbacks.« less

Molecular Insights into Arctic Soil Organic Matter Degradation under Warming

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

Chen, Hongmei; Yang, Ziming; Chu, Rosalie K.

Molecular composition of the Arctic soil organic carbon (SOC) and its susceptibility to microbial degradation are uncertain due to heterogeneity and unknown SOC compositions. By using ultrahigh-resolution mass spectrometry, we determined the susceptibility and compositional changes of extractable dissolved organic matter (EDOM) in an anoxic warming incubation experiment (up to 122 days) with a tundra soil from Alaska (United States). EDOM was extracted with 10 mM NH 4HCO 3 from both the organic- and mineral-layer soils during incubation at both -2 and 8°C. Based on their O:C and H:C ratios, EDOM molecular formulas were qualitatively grouped into nine biochemical classesmore » of compounds, among which lignin-like compounds dominated both the organic and the mineral soils and were the most stable, whereas amino sugars, peptides, and carbohydrate-like compounds were the most biologically labile. These results corresponded with shifts in EDOM elemental composition in which the ratios of O:C and N:C decreased, while the average C content in EDOM, molecular mass, and aromaticity increased after 122 days of incubation. This research demonstrates that certain EDOM components, such as amino sugars, peptides, and carbohydrate-like compounds, are disproportionately more susceptible to microbial degradation than others in the soil, and these results should be considered in SOC degradation models to improve predictions of Arctic climate feedbacks.« less

Variability of hazardous air pollutants in an urban area

NASA Astrophysics Data System (ADS)

Spicer, Chester W.; Buxton, Bruce E.; Holdren, Michael W.; Smith, Deborah L.; Kelly, Thomas J.; Rust, Steven W.; Pate, Alan D.; Sverdrup, George M.; Chuang, Jane C.

The variability of hazardous air pollutants (HAPs) is an important factor in determining human exposure to such chemicals, and in designing HAP measurement programs. This study has investigated the factors which contribute to HAP variability in an urban area. Six measurement sites separated by up to 12 km collected data with 3 h time resolution to examine spatial variability within neighborhoods and between neighborhoods. The measurements were made in Columbus, OH. The 3 h results also were used to study temporal variability, and duplicate samples collected at each site were used to determine the component of variability attributable to the measurement process. Hourly samples collected over 10 days at one site provided further insight into the temporal resolution needed to capture short-term peak concentrations. Measurements at the 6 spatial sites focused on 78 chemicals. Twenty-three of these species were found in at least 95% of the 3 h samples, and 39 chemicals were present at least 60% of the time. The relative standard deviations for most of these 39 frequently detected chemicals was 1.0 or lower. Variability was segmented into temporal, spatial, and measurement components. Temporal variation was the major contributor to HAP variability for 19 of the 39 frequently detected compounds, based on the 3 h data. Measurement imprecision contributed less than 25% for most of the volatile organic species, but 30% or more of the variability for carbonyl compounds, trace elements, and particle-bound extractable organic mass. Interestingly, the spatial component contributed less than 20% of the total variability for all the chemicals except sulfur. Based on the data with hourly resolution, peak to median ratios (hourly peak to 24 h median) averaged between 2 and 4 for most of the volatile organic compounds, but there were two species with peak to median ratios of about 10.

Isolation of Purines and Pyrimidines from the Murchison Meteorite

NASA Technical Reports Server (NTRS)

Glavin, D. P.; Bada, J. K.

2003-01-01

The origin of life on Earth, and possibly on other planets such as Mars, would have required the presence of liquid water and a continuous supply of prebiotic organic compounds. The delivery of organic matter by asteroids, comets, and carbonaceous meteorites could have contributed to the early Earth's prebiotic inventory by seeding the planet with biologically important organic compounds. A wide variety of prebiotic organic compounds have previously been detected in the Murchison CM type carbonaceous chondrite including amino acids, purines and pyrimidines'. These compounds play a major role in terrestrial biochemistry and are integral components of proteins, DNA and RNA. In this study we developed a new extraction technique using sublimation in order to isolate purines and pyrimidines from Murchison2, which is cleaner and more time efficient that traditional methods3. Several purines including adenine, guanine, hypoxanthine and xanthine were positively identified by high performance liquid chromatography and ultraviolet absorption detection in our Murchison extracts. The purines detected in Murchison do not correlate with the distribution of nucleobases found in geological environments on Earth4. Moreover, the abundance of extraterrestrial amino acids and the low level of terrestrial amino acid contaminants found in Murchison', support the idea that the purines in t h s meteorite are extraterrestrial in origin.

Prospects for reconstructing paleoenvironmental conditions from organic compounds in polar snow and ice

USGS Publications Warehouse

Giorio, Chiara; Kehrwald, Natalie; Barbante, Carlo; Kalberer, Markus; King, Amy C.F.; Thomas, Elizabeth R.; Wolff, Eric W.; Zennaro, Piero

2018-01-01

Polar ice cores provide information about past climate and environmental changes over periods ranging from a few years up to 800,000 years. The majority of chemical studies have focused on determining inorganic components, such as major ions and trace elements as well as on their isotopic fingerprint. In this paper, we review the different classes of organic compounds that might yield environmental information, discussing existing research and what is needed to improve knowledge. We also discuss the problems of sampling, analysis and interpretation of organic molecules in ice. This review highlights the great potential for organic compounds to be used as proxies for anthropogenic activities, past fire events from different types of biomass, terrestrial biogenic emissions and marine biological activity, along with the possibility of inferring past temperature fluctuations and even large-scale climate variability. In parallel, comprehensive research needs to be done to assess the atmospheric stability of these compounds, their ability to be transported long distances in the atmosphere, and their stability in the archive in order to better interpret their fluxes in ice cores. In addition, specific decontamination procedures, analytical methods with low detection limits (ng/L or lower), fast analysis time and low sample requests need to be developed in order to ensure a good time resolution in the archive.

A Pilot Study Exploring the Use of Breath Analysis to Differentiate Healthy Cattle from Cattle Experimentally Infected with Mycobacterium bovis

PubMed Central

Ellis, Christine K.; Stahl, Randal S.; Nol, Pauline; Waters, W. Ray; Palmer, Mitchell V.; Rhyan, Jack C.; VerCauteren, Kurt C.; McCollum, Matthew; Salman, M. D.

2014-01-01

Bovine tuberculosis, caused by Mycobacterium bovis, is a zoonotic disease of international public health importance. Ante-mortem surveillance is essential for control; however, current surveillance tests are hampered by limitations affecting ease of use or quality of results. There is an emerging interest in human and veterinary medicine in diagnosing disease via identification of volatile organic compounds produced by pathogens and host-pathogen interactions. The objective of this pilot study was to explore application of existing human breath collection and analysis methodologies to cattle as a means to identify M. bovis infection through detection of unique volatile organic compounds or changes in the volatile organic compound profiles present in breath. Breath samples from 23 male Holstein calves (7 non-infected and 16 M. bovis-infected) were collected onto commercially available sorbent cartridges using a mask system at 90 days post-inoculation with M. bovis. Samples were analyzed using gas chromatography-mass spectrometry, and chromatographic data were analyzed using standard analytical chemical and metabolomic analyses, principle components analysis, and a linear discriminant algorithm. The findings provide proof of concept that breath-derived volatile organic compound analysis can be used to differentiate between healthy and M. bovis-infected cattle. PMID:24586655

Prospects for reconstructing paleoenvironmental conditions from organic compounds in polar snow and ice

NASA Astrophysics Data System (ADS)

Giorio, Chiara; Kehrwald, Natalie; Barbante, Carlo; Kalberer, Markus; King, Amy C. F.; Thomas, Elizabeth R.; Wolff, Eric W.; Zennaro, Piero

2018-03-01

Polar ice cores provide information about past climate and environmental changes over periods ranging from a few years up to 800,000 years. The majority of chemical studies have focused on determining inorganic components, such as major ions and trace elements as well as on their isotopic fingerprint. In this paper, we review the different classes of organic compounds that might yield environmental information, discussing existing research and what is needed to improve knowledge. We also discuss the problems of sampling, analysis and interpretation of organic molecules in ice. This review highlights the great potential for organic compounds to be used as proxies for anthropogenic activities, past fire events from different types of biomass, terrestrial biogenic emissions and marine biological activity, along with the possibility of inferring past temperature fluctuations and even large-scale climate variability. In parallel, comprehensive research needs to be done to assess the atmospheric stability of these compounds, their ability to be transported long distances in the atmosphere, and their stability in the archive in order to better interpret their fluxes in ice cores. In addition, specific decontamination procedures, analytical methods with low detection limits (ng/L or lower), fast analysis time and low sample requests need to be developed in order to ensure a good time resolution in the archive.

Effect of selected organic and inorganic snow and cloud components on the photochemical generation of nitrite by nitrate irradiation.

PubMed

Minero, Claudio; Maurino, Valter; Bono, Francesca; Pelizzetti, Ezio; Marinoni, Angela; Mailhot, Gilles; Carlotti, Maria Eugenia; Vione, Davide

2007-08-01

The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging.

Anthropogenic Pollutants in Extracts from Maritsa Iztok Dumps

NASA Astrophysics Data System (ADS)

Stefanova, Maya; Milakovska, Zlatka; Marinov, Stefan

2017-12-01

Coals are suspected for many human health problems and are an object of the new discipline - “medical geology”. Potential human health risk of organic compounds with coal/lignite provenance includes endocrine disruption, nephrotoxicity, cancer, etc. Recent investigations proved that different organic components, i.e. hydrocarbons, phenols etc. move through/release out of the dump area as a result of alteration processes of the organic matter (OM) caused by the wash-out and/or drainage processes. The timeliness of the present study is based on the scarcity of information on organic geochemistry of dump materials from open pit coal mines and weathered lignites in particular. The limited number of studies on dumps clarifies that even for the “short” time span (some tens of years) in geological point of view, processes of transformation of the extractable OM are detectable. The secondary phases, a result of the OM transformations, move through and out of the dump area and could be potential contaminants for the surface/underground waters and soils in the area. Another environmental problem comes from the air-born VOCs and products of the modern chemical industry. By GC-MS in the slightly polar fractions of the chloroform extracts of dump samples a broad set of components was determined, i.e. phthalates (dominant), i-propyl palmitate, i-propyl myristate, n-hexyl benzoates, etc. These organic contaminants could be regarded more likely as anthropogenic (originating from plasticizers, industrial pollutants, etc.). Presently, it seems that the identified compounds do not represent an acute toxic risk from an environmental viewpoint. However, some compounds could raise concerns and further attention is needed to be focused on them.

Relating the Chemical Composition of Dissolved Organic Matter Draining Permafrost Soils to its Photochemical Degradation in Arctic Surface Waters.

NASA Astrophysics Data System (ADS)

Ward, C.; Cory, R. M.

2015-12-01

Thawing permafrost soils are expected to shift the chemical composition of DOM exported to and degraded in arctic surface waters. While DOM photo-degradation is an important component of the freshwater C cycle in the Arctic, the molecular controls on DOM photo-degradation remain poorly understood, making it difficult to predict how shifting chemical composition may alter DOM photo-degradation in arctic surface waters. To address this knowledge gap, we quantified the susceptibility of DOM draining the shallow organic mat and the deeper permafrost layer to complete photo-oxidation to CO₂ and partial photo-oxidation to compounds that remain in the DOM pool, and investigated changes in DOM chemical composition following sunlight exposure. DOM leached from the organic mat contained higher molecular weight, more oxidized and unsaturated aromatic species compared to permafrost DOM. Despite significant differences in initial chemical composition, permafrost and organic mat DOM had similar susceptibilities to complete photo-oxidation to CO₂. Concurrent losses of carboxyl moieties and shifts in chemical composition during photo-degradation indicated that carboxyl-rich tannin-like compounds in both DOM sources were likely photo-decarboxylated to CO₂. Permafrost DOM had a higher susceptibility to partial photo-oxidation compared to organic mat DOM, potentially due to a lower abundance of phenolic compounds that act as "antioxidants" and slow the oxidation of DOM. These results demonstrated how chemical composition controls the photo-degradation of DOM in arctic surface waters, and that DOM photo-degradation will likely remain an important component of the freshwater C budget in the Arctic with increased export of permafrost DOM to surface waters.

Identification of compounds in an anti-fibrosis Chinese medicine (Fufang Biejia Ruangan Pill) and its absorbed components in rat biofluids and liver by UPLC-MS.

PubMed

Dong, Qin; Qiu, Ling-Ling; Zhang, Cong-En; Chen, Long-Hu; Feng, Wu-Wen; Ma, Li-Na; Yan, Dan; Niu, Ming; Wang, Jia-Bo; Xiao, Xiao-He

2016-07-15

Liver fibrosis represents a major public health problem worldwide. To date, antifibrotic treatment of fibrosis still remains an unconquered area for western medicine. Fufang Biejia Ruangan Pill (FFBJ) is the first anti-fibrosis drug approved by the China State Food and Drug Administration, and has been demonstrated to have a good antifibrotic efficacy in China. However, the chemical constituents of FFBJ and the absorption and distribution of it in vivo remain unclear, which restricts its research on bioactive components identification and mechanisms of action. In this study, ultra-performance liquid chromatography/quadrupole-time-of-flight mass spectrometry (UPLC/Q-TOF-MS) combined with ultra-performance liquid chromatography/triple quadrupole mass spectrometry (UPLC/QqQ-MS) was applied to identify compounds in FFBJ and its absorbed components in rat serum, liver and urine samples after intragastric administration of FFBJ. As a result, a total of 32 Chinese material medica components including organic acids, terpenoids, flavonoids, phenylpropanoids and alkaloids, were identified or tentatively characterized, while the distribution of 10 prototype compounds in rat serum, liver and urine were discovered. The identified constituents in FFBJ and the distribution of prototype compounds in rat serum, liver and urine are help for understanding the material bases of its therapeutic effects. Copyright © 2016. Published by Elsevier B.V.

[Total analysis of organic rubber additives].

PubMed

He, Wen-Xuan; Robert, Shanks; You, Ye-Ming

2010-03-01

In the present paper, after middle pressure chromatograph separation using both positive phase and reversed-phase conditions, the organic additives in ethylene-propylene rubber were identified by infrared spectrometer. At the same time, by using solid phase extraction column to maintain the main component-fuel oil in organic additves to avoid its interfering with minor compounds, other organic additves were separated and analysed by GC/Ms. In addition, the remaining active compound such as benzoyl peroxide was identified by CC/Ms, through analyzing acetone extract directly. Using the above mentioned techniques, soften agents (fuel oil, plant oil and phthalte), curing agent (benzoylperoxide), vulcanizing accelerators (2-mercaptobenzothiazole, ethyl thiuram and butyl thiuram), and antiagers (2, 6-Di-tert-butyl-4-methyl phenol and styrenated phenol) in ethylene-propylene rubber were identified. Although the technique was established in ethylene-propylene rubber system, it can be used in other rubber system.

Sustainable Materials for Sustainable Energy Storage: Organic Na Electrodes

PubMed Central

Oltean, Viorica-Alina; Renault, Stéven; Valvo, Mario; Brandell, Daniel

2016-01-01

In this review, we summarize research efforts to realize Na-based organic materials for novel battery chemistries. Na is a more abundant element than Li, thereby contributing to less costly materials with limited to no geopolitical constraints while organic electrode materials harvested from biomass resources provide the possibility of achieving renewable battery components with low environmental impact during processing and recycling. Together, this can form the basis for truly sustainable electrochemical energy storage. We explore the efforts made on electrode materials of organic salts, primarily carbonyl compounds but also Schiff bases, unsaturated compounds, nitroxides and polymers. Moreover, sodiated carbonaceous materials derived from biomasses and waste products are surveyed. As a conclusion to the review, some shortcomings of the currently investigated materials are highlighted together with the major limitations for future development in this field. Finally, routes to move forward in this direction are suggested. PMID:28773272

Sustainable Materials for Sustainable Energy Storage: Organic Na Electrodes.

PubMed

Oltean, Viorica-Alina; Renault, Stéven; Valvo, Mario; Brandell, Daniel

2016-03-01

In this review, we summarize research efforts to realize Na-based organic materials for novel battery chemistries. Na is a more abundant element than Li, thereby contributing to less costly materials with limited to no geopolitical constraints while organic electrode materials harvested from biomass resources provide the possibility of achieving renewable battery components with low environmental impact during processing and recycling. Together, this can form the basis for truly sustainable electrochemical energy storage. We explore the efforts made on electrode materials of organic salts, primarily carbonyl compounds but also Schiff bases, unsaturated compounds, nitroxides and polymers. Moreover, sodiated carbonaceous materials derived from biomasses and waste products are surveyed. As a conclusion to the review, some shortcomings of the currently investigated materials are highlighted together with the major limitations for future development in this field. Finally, routes to move forward in this direction are suggested.

"Sweeter than a rose", at least to Triatoma phyllosoma complex males (Triatominae: Reduviidae).

PubMed

May-Concha, Irving J; Cruz-López, Leopoldo C; Rojas, Julio C; Ramsey, Janine M

2018-02-17

The Triatoma phyllosoma complex of Trypanosoma cruzi vectors (Triatominae: Reduviidae) is distributed in both Neotropical and Nearctic bioregions of Mexico. Volatile organic compounds emitted by disturbed Triatoma longipennis, Triatoma pallidipennis and Triatoma phyllosoma, and from their Brindley's and metasternal glands, were identified using solid-phase microextraction coupled with gas chromatography-mass spectrometry. Disturbed bugs and the metasternal glands from T. phyllosoma released or had significantly fewer compounds than T. longipennis and T. pallidipennis. Isobutyric acid was the most abundant compound secreted by disturbed bugs of the three species, while Brindley's glands of all species produced another four compounds: propanoic acid, isobutyric acid, pentyl butanoate, and 2-methyl hexanoic acid. Two novel compounds, both rose oxide isomers, were produced in MGs and released only by disturbed females of all three species, making this the first report in Triatominae of these monoterpenes. The principal compound in MGs of both sexes of T. longipennis and T. phyllosoma was 3-methyl-2-hexanone, while cis-rose oxide was the principal compound in T. pallidipennis females. The major components in male effluvia of T. pallidipennis were 2-decanol and 3-methyl-2-hexanone. Discriminant analysis of volatile organic compounds was significant, separating the three species and was consistent with morphological and genetic evidence for species distinctions within the complex.

Infrared mapping resolves soft tissue preservation in 50 million year-old reptile skin.

PubMed

Edwards, N P; Barden, H E; van Dongen, B E; Manning, P L; Larson, P L; Bergmann, U; Sellers, W I; Wogelius, R A

2011-11-07

Non-destructive Fourier Transform InfraRed (FTIR) mapping of Eocene aged fossil reptile skin shows that biological control on the distribution of endogenous organic components within fossilized soft tissue can be resolved. Mapped organic functional units within this approximately 50 Myr old specimen from the Green River Formation (USA) include amide and sulphur compounds. These compounds are most probably derived from the original beta keratin present in the skin because fossil leaf- and other non-skin-derived organic matter from the same geological formation do not show intense amide or thiol absorption bands. Maps and spectra from the fossil are directly comparable to extant reptile skin. Furthermore, infrared results are corroborated by several additional quantitative methods including Synchrotron Rapid Scanning X-Ray Fluorescence (SRS-XRF) and Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS). All results combine to clearly show that the organic compound inventory of the fossil skin is different from the embedding sedimentary matrix and fossil plant material. A new taphonomic model involving ternary complexation between keratin-derived organic molecules, divalent trace metals and silicate surfaces is presented to explain the survival of the observed compounds. X-ray diffraction shows that suitable minerals for complex formation are present. Previously, this study would only have been possible with major destructive sampling. Non-destructive FTIR imaging methods are thus shown to be a valuable tool for understanding the taphonomy of high-fidelity preservation, and furthermore, may provide insight into the biochemistry of extinct organisms.

Infrared mapping resolves soft tissue preservation in 50 million year-old reptile skin

PubMed Central

Edwards, N. P.; Barden, H. E.; van Dongen, B. E.; Manning, P. L.; Larson, P. L.; Bergmann, U.; Sellers, W. I.; Wogelius, R. A.

2011-01-01

Non-destructive Fourier Transform InfraRed (FTIR) mapping of Eocene aged fossil reptile skin shows that biological control on the distribution of endogenous organic components within fossilized soft tissue can be resolved. Mapped organic functional units within this approximately 50 Myr old specimen from the Green River Formation (USA) include amide and sulphur compounds. These compounds are most probably derived from the original beta keratin present in the skin because fossil leaf- and other non-skin-derived organic matter from the same geological formation do not show intense amide or thiol absorption bands. Maps and spectra from the fossil are directly comparable to extant reptile skin. Furthermore, infrared results are corroborated by several additional quantitative methods including Synchrotron Rapid Scanning X-Ray Fluorescence (SRS-XRF) and Pyrolysis-Gas Chromatography/Mass Spectrometry (Py-GC/MS). All results combine to clearly show that the organic compound inventory of the fossil skin is different from the embedding sedimentary matrix and fossil plant material. A new taphonomic model involving ternary complexation between keratin-derived organic molecules, divalent trace metals and silicate surfaces is presented to explain the survival of the observed compounds. X-ray diffraction shows that suitable minerals for complex formation are present. Previously, this study would only have been possible with major destructive sampling. Non-destructive FTIR imaging methods are thus shown to be a valuable tool for understanding the taphonomy of high-fidelity preservation, and furthermore, may provide insight into the biochemistry of extinct organisms. PMID:21429928

Abiogenic photochemical synthesis on surface of meteorites and other small space bodies

NASA Astrophysics Data System (ADS)

Simakov, Michael B.; Kuzicheva, Eugenia A.

The abiogenic photochemical synthesis of complex biochemical compounds on the surface of small bodies in our Solar system was examined. Hydrated minerals are found within a chondrite matrix of meteorites together with significant amounts of organic matter. Clays are likely to have formed when water was present on parent meteoritic bodies. In order to verify the existence of a relationship between abiogenic synthesis of nucleotides and inorganic components of the meteorites, we have investigated possible abiogenic reactions associated with different clay (montmorillonite, kaolinite) and a basaltic one (Tyatya's volcanic ash) under action of open space energy sources as a model of different exobiological environments on the surface of small space bodies. The abiogenic synthesis of natural adenine nucleotides from a mixture of adenosine and inorganic phosphate has been observed following irradiation with VUV light in the presence of different mineral samples. The yields of the products (5'AMP, 2'AMP, 3'AMP, 2'3'cAMP and 3'5'cAMP) depended on irradiation time and kinds of minerals used. The discovery that meteoritic organic compounds may be trapped and protected within a clay mineral matrix has implications for our understanding of prebiotic molecular evolution in the early Solar system. Clay minerals may also have concentrated organic compounds thereby promoting polymerization reactions. An adsorption/binding of nucleic acids components by clay crystals could change the electron distribution and/or the conformation of the molecules. The remnant water molecules in the clay sheets also could influence the course of the reaction. Clay immobilization of phosphate could play an important role in this reaction. Chondritic material could have been a common component of the inner Solar system shortly after its formation and the biologically useful products of clay mineral-organic matter interactions could have also widespread, and delivered to planetary surfaces through the accretion of carbonaceous asteroids.

An abiogenic photochemical synthesis on surface of meteorites and other small space bodies

NASA Astrophysics Data System (ADS)

Simakov, M.; Kuzicheva, E.

Abiogenic photochemical synthesis of complex biochemical compounds on the surface of small bodies in our Solar system was examined. The hydrated minerals are found within a chondrite matrix of meteorites together with significant amounts of organic matter. Clays are likely to have formed when water was presented on parent meteoritic bodies. In order to verify the existence of a relationship between abiogenic synthesis of nucleotides and inorganic components of the meteorites we have investigated possible abiogenic reactions at the presence of different clay minerals (montmorillonite, kaolinite) and basaltic sample (Tjatja's volcanic ash) under action of open space energy sources for modeling of different exobiological environments on the surface of small space bodies. The abiogenic synthesis of natural adenine nucleotides from mixture of adenosine plus inorganic phosphate has been observed under an irradiation with VUV radiation at the presence of different mineral samples. The yields of the products (5'AMP, 2'AMP, 3'AMP, 2'3'cAMP and 3'5'cAMP) were depended from irradiation time and kind of used minerals. The discovery that meteoritic organic compounds may be trapped and protected within a clay mineral matrix has implications for our understanding of prebiotic molecular evolution in the early Solar system. Clay minerals may have concentrated organic compounds thereby promoting polymerization reactions also. An adsorption/binding of nucleic acids components by clay crystals could change in the electron distribution and/or the conformation of the molecules. The remnant water molecules in the clay sheets also could influence on the course of the reaction. Besides, an immobilization of phosphate on clay also could play an important role in our reaction. Chondritic material would have been a common component of the inner Solar system shortly after its formation and the biologically useful products of clay mineral-organic matter interactions would have also widespread, and delivered to planetary surfaces through the accretion of carbonaceous asteroids.

Seven organic salts assembled from hydrogen-bonds of N-H⋯O, O-H⋯O, and C-H⋯O between acidic compounds and bis(benzimidazole)

NASA Astrophysics Data System (ADS)

Jin, Shouwen; Liu, Hui; Gao, Xin Jun; Lin, Zhanghui; Chen, Guqing; Wang, Daqi

2014-10-01

Seven crystalline organic acid-base adducts derived from 1,4-bis(benzimidazol-2-yl)butane/1,2-bis(2-benzimidazolyl)-1,2-ethanediol and acidic components (picric acid, 2-hydroxy-5-(phenyldiazenyl)benzoic acid, 5-sulfosalicylic acid, oxalic acid, and 1,5-naphthalenedisulfonic acid) were prepared and characterized by the single crystal X-ray diffraction analysis, IR, mp, and elemental analysis. All of the seven compounds are organic salts involving proton transfer from the acidic components to the bis(benzimidazole). For the salt 3, although a competing carboxyl group is present, it has been observed that only the proton at the -SO3H group is deprotonized rather than the H at the COOH. While in the salt 7, both COOH and SO3H were ionized to exhibit a valence number of -2. For 4, the oxalic acid existed as unionized molecule, monoanion, and dianion simultaneously in one compound. All supramolecular architectures of the organic salts 1-7 involve extensive intermolecular N-H⋯O, O-H⋯O, and C-H⋯O hydrogen bonds as well as other noncovalent interactions. Since the potentially hydrogen bonding phenol group is present in the ortho position to the carboxyl group in 2, 3, and 7, it forms the more facile intramolecular O-H⋯O hydrogen bonding. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. These weak interactions combined, all the complexes displayed 3D framework structure.

EMISSIONS FROM COATINGS USED IN THE AUTO REFINISHING INDUSTRY

EPA Science Inventory

The report presents results of EPA Methods 24 and 311 analyses of the volatile organic compound (VOC) content of selected auto refinishing coatings and their components that are sold by the five major auto coating manufacturers. These analyses were undertaken to determine the acc...

MEASUREMENT OF VOLATILE ORGANIC COMPOUNDS IN EXHALED BREATH AS COLLECTED IN EVACUATED ELECTROPOLISHED CANISTERS

EPA Science Inventory

A set of three complementary analytical methods were developed specifically for exhaled breath as collected in evacuated stainless steel canisters using gas chromatography - mass spectrometry detection. The first is a screening method to quantify the carbon dioxide component (gen...

Origins and identities of key manure odor components

USDA-ARS?s Scientific Manuscript database

Odor is just one of many environmental issues associated with animal manures. Odor arises from a number of different locations in animal production systems, but the chemistry and biochemical origin is similar across sites. A complex mixture of volatile organic compounds (VOC) and inorganic compoun...

40 CFR 59.100 - Applicability and designation of regulated entity.

Code of Federal Regulations, 2013 CFR

2013-07-01

... COMMERCIAL PRODUCTS National Volatile Organic Compound Emission Standards for Automobile Refinish Coatings... automobile refinish coatings and coating components manufactured on or after January 11, 1999 for sale or distribution in the United States. (b) Regulated entities are manufacturers and importers of automobile...

40 CFR 59.100 - Applicability and designation of regulated entity.

Code of Federal Regulations, 2014 CFR

2014-07-01

... COMMERCIAL PRODUCTS National Volatile Organic Compound Emission Standards for Automobile Refinish Coatings... automobile refinish coatings and coating components manufactured on or after January 11, 1999 for sale or distribution in the United States. (b) Regulated entities are manufacturers and importers of automobile...

40 CFR 59.100 - Applicability and designation of regulated entity.

Code of Federal Regulations, 2012 CFR

2012-07-01

... COMMERCIAL PRODUCTS National Volatile Organic Compound Emission Standards for Automobile Refinish Coatings... automobile refinish coatings and coating components manufactured on or after January 11, 1999 for sale or distribution in the United States. (b) Regulated entities are manufacturers and importers of automobile...

EVALUATION OF BIOAEROSOL COMPONENTS, GENERATION FACTORS, AND AIRBORNE TRANSPORT ASSOCIATED WITH LIME TREATMENT OF CONTAMINATED SEDIMENT

EPA Science Inventory

Lime treatment has been used in contaminated sediment management activities for many purposes such as dewatering, improvement of physical properties, and reducing contaminant mobility. Exothermic volatilization of volatile organic compounds from lime-treated sediment is well kno...

[Emission Characteristics of VOCs from Typical Restaurants in Beijing].

PubMed

Cui, Tong; Cheng, Jing-chen; He, Wan-qing; Ren, Pei-fang; Nie, Lei; Xu, Dong-yao; Pan, Tao

2015-05-01

Using the EPA method, emission of volatile organic compounds (VOCs) , sampled from barbecue, Chinese and Western fast-food, Sichuan cuisine and Zhejiang cuisine restaurants in Beijing was investigated. VOCs concentrations and components from different cuisines were studied. The results indicated that based on the calibrated baseline ventilation volume, the VOCs emission level from barbecue was the highest, reaching 12.22 mg · m(-3), while those from fast-food of either Chinese or Western, Sichuan cuisine and Zhejiang cuisine were about 4 mg · m(-3). The components of VOCs from barbecue were different from those in the other cuisines, which were mainly propylene, 1-butene, n-butane, etc. The non-barbecue cuisines consisted of high concentration of alcohols, and Western fast-food contained relatively high proportion of aldehydes and ketones organic compounds. According to emission concentration of baseline ventilation volume, barbecue released more pollutants than the non-barbecue cuisines at the same scale. So, barbecue should be supervised and controlled with the top priority.

Source apportionment of exposures to volatile organic compounds. I. Evaluation of receptor models using simulated exposure data

NASA Astrophysics Data System (ADS)

Miller, Shelly L.; Anderson, Melissa J.; Daly, Eileen P.; Milford, Jana B.

Four receptor-oriented source apportionment models were evaluated by applying them to simulated personal exposure data for select volatile organic compounds (VOCs) that were generated by Monte Carlo sampling from known source contributions and profiles. The exposure sources modeled are environmental tobacco smoke, paint emissions, cleaning and/or pesticide products, gasoline vapors, automobile exhaust, and wastewater treatment plant emissions. The receptor models analyzed are chemical mass balance, principal component analysis/absolute principal component scores, positive matrix factorization (PMF), and graphical ratio analysis for composition estimates/source apportionment by factors with explicit restriction, incorporated in the UNMIX model. All models identified only the major contributors to total exposure concentrations. PMF extracted factor profiles that most closely represented the major sources used to generate the simulated data. None of the models were able to distinguish between sources with similar chemical profiles. Sources that contributed <5% to the average total VOC exposure were not identified.

The major bioactive components of seaweeds and their mosquitocidal potential.

PubMed

Yu, Ke-Xin; Jantan, Ibrahim; Ahmad, Rohani; Wong, Ching-Lee

2014-09-01

Seaweeds are one of the most widely studied natural resources for their biological activities. Novel seaweed compounds with unique chemical structures have been reported for their pharmacological properties. The urge to search for novel insecticidal compound with a new mode of action for development of botanical insecticides supports the relevant scientific research on discovering the bioactive compounds in seaweeds. The mosquitocidal potential of seaweed extracts and their isolated compounds are documented in this review paper, along with the discussion on bioactivities of the major components of seaweeds such as polysaccharides, phenolics, proteins, terpenes, lipids, and halogenated compounds. The effects of seaweed extracts and compounds toward different life stages of mosquito (egg, larva, pupa, and adult), its growth, development, and reproduction are elaborated. The structure-activity relationships of mosquitocidal compounds are discussed to extrapolate the possible chemical characteristics of seaweed compounds responsible for insecticidal properties. Furthermore, the possible target sites and mode of actions of the mosquitocidal seaweed compounds are included in this paper. The potential synergistic effects between seaweeds and commercial insecticides as well as the toxic effects of seaweed extracts and compounds toward other insects and non-target organisms in the same habitat are also described. On top of that, various factors that influence the mosquitocidal potential of seaweeds, such as abiotic and biotic variables, sample preparation, test procedures, and considerations for a precise experimental design are discussed. The potential of active seaweed extracts and compounds in the development of effective bioinsecticide are also discussed.

Seasonal variation of organic aerosol in PM2.5 at Anmyeondo, a background site in Korea

NASA Astrophysics Data System (ADS)

Lee, J.; Kim, E. S.; Kim, Y. P.; Jung, C. H.; Lee, J.

2016-12-01

Routine measurements of PM2.5 and chemical speciation for 100 individual organic compounds were carried out to understand seasonal variation of organic compounds at a background area in Korea between 2015 and 2016. Organic compounds analyzed in this study were classified into five groups, n-alkanes, polycyclic aromatic hydrocarbons (PAHs), fatty acids (FA), dicarboxylic acids (DCAs), and sugar. Further, organic carbon (OC), elemental carbon (EC), water-soluble organic carbon (WSOC) and Humic Like Substance-Carbon (HULIS-C) in PM2.5 were simultaneously analyzed to make mass balance of carbonaceous aerosol in PM2.5 at a background site in Korea. PAHs concentrations at this site was lower than that at Seoul, a representative urban site in Korea. PAHs and n-Alkanes concentrations showed clear seasonal variation with summer minimum and winter maximum, while, seasonal variation of DCAs and Sugars were different with PAHs and n-Alkanes.WSOC concentrations were highly correlated with SOC (Secondary Organic Carbon) concentrations which were estimated by the EC tracer method. The results indicate the formation of secondary organic aerosol (SOA) is major factor for the determination of WSOC concentrations in this region. HULIS-C as known one of brown carbon was major component of WSOC which accounts for 39 to 99% in WSOC. The average concentrations of HULIS-C was 2.02±1.42 and the highest concentration was observed in fall.

High Molecular Weight Petrogenic and Pyrogenic Hydrocarbons in Aquatic Environments

NASA Astrophysics Data System (ADS)

Abrajano, T. A., Jr.; Yan, B.; O'Malley, V.

2003-12-01

Geochemistry is ultimately the study of sources, movement, and fate of chemicals in the geosphere at various spatial and temporal scales. Environmental organic geochemistry focuses such studies on organic compounds of toxicological and ecological concern (e.g., Schwarzenbach et al., 1993, 1998; Eganhouse, 1997). This field emphasizes not only those compounds with potential toxicological properties, but also the geological systems accessible to the biological receptors of those hazards. Hence, the examples presented in this chapter focus on hydrocarbons with known health and ecological concern in accessible shallow, primarily aquatic, environments.Modern society depends on oil for energy and a variety of other daily needs, with present mineral oil consumption throughout the 1990s exceeding 3×109 t yr-1 (NRC, 2002). In the USA, e.g., ˜40% of energy consumed and 97% of transportation fuels are derived from oil. In the process of extraction, refinement, transport, use, and waste production, a small but environmentally significant fraction of raw oil materials, processed products, and waste are released inadvertently or purposefully into the environment. Because their presence and concentration in the shallow environments are often the result of human activities, these organic materials are generally referred to as "environmental contaminants." Although such reference connotes some form of toxicological or ecological hazard, specific health or ecological effects of many organic "environmental contaminants" remain to be demonstrated. Some are, in fact, likely innocuous at the levels that they are found in many systems, and simply adds to the milieu of biogenic organic compounds that naturally cycle through the shallow environment. Indeed, virtually all compounds in crude oil and processed petroleum products have been introduced naturally to the shallow environments as oil and gas seepage for millions of years ( NRC, 2002). Even high molecular weight (HMW) polyaromatic compounds were introduced to shallow environments through forest fires and natural coking of crude oil ( Ballentine et al., 1996; O'Malley et al., 1997). The full development of natural microbial enzymatic systems that can utilize HMW hydrocarbons as carbon or energy source attests to the antiquity of hydrocarbon dispersal processes in the environment. The environmental concern is, therefore, primarily due to the rate and spatial scale by which petroleum products are released in modern times, particularly with respect to the environmental sensitivity of some ecosystems to these releases ( Schwarzenbach et al., 1993; Eganhouse, 1997; NRC, 2002).Crude oil is produced by diagenetic and thermal maturation of terrestrial and marine plant and animal materials in source rocks and petroleum reservoirs. Most of the petroleum in use today is produced by thermal and bacterial decomposition of phytoplankton material that once lived near the surface of the world's ocean, lake, and river waters (Tissot and Welte, 1984). Terrestrially derived organic matter can be regionally significant, and is the second major contributor to the worldwide oil inventory ( Tissot and Welte, 1984; Peters and Moldowan, 1993; Engel and Macko, 1993). The existing theories hold that the organic matter present in crude oil consists of unconverted original biopolymers and new compounds polymerized by reactions promoted by time and increasing temperature in deep geologic formations. The resulting oil can migrate from source to reservoir rocks where the new geochemical conditions may again lead to further transformation of the petrogenic compounds. Any subsequent changes in reservoir conditions brought about by uplift, interaction with aqueous fluids, or even direct human intervention (e.g., drilling, water washing) likewise could alter the geochemical makeup of the petrogenic compounds. Much of our understanding of environmental sources and fate of hydrocarbon compounds in shallow environments indeed borrowed from the extensive geochemical and analytical framework that was meticulously built by petroleum geochemists over the years (e.g., Tissot and Welte, 1984; Peters et al., 1992; Peters and Moldowan, 1993; Engel and Macko, 1993; Moldowan et al., 1995; Wang et al., 1999; Faksness et al., 2002).Hydrocarbon compounds present in petroleum or pyrolysis by-products can be classified based on their composition, molecular weight, organic structure, or some combination of these criteria. For example, a report of the Committee on Intrinsic Remediation of the US NRC classified organic contaminants into HMW hydrocarbons, low molecular weight (LMW) hydrocarbons, oxygenated hydrocarbons, halogenated aliphatics, halogenated aromatics, and nitroaromatics (NRC, 2000). Hydrocarbons are compounds comprised exclusively of carbon and hydrogen and they are by far the dominant components of crude oil, processed petroleum hydrocarbons (gasoline, diesel, kerosene, fuel oil, and lubricating oil), coal tar, creosote, dyestuff, and pyrolysis waste products. These hydrocarbons often occur as mixtures of a diverse group of compounds whose behavior in near-surface environments is governed by their chemical structure and composition, the geochemical conditions and media of their release, and biological factors, primarily microbial metabolism, controlling their transformation and degradation.Hydrocarbons comprise from 50% to 99% of compounds present in refined and unrefined oil, and compounds containing other elements such as oxygen, nitrogen, and sulfur are present in relatively smaller proportions. Hydrocarbon compounds have carbons joined together as single C - C bonds (i.e., alkanes), double or triple C=C bonds (i.e., alkenes or olefins), or via an aromatic ring system with resonating electronic structure (i.e., aromatics). Alkanes, also called paraffins, are the dominant component of crude oil, with the carbon chain forming either straight (n-alkanes), branched (iso-alkanes), or cyclic (naphthenes) arrangement of up to 60 carbons (Figure 1). Aromatic compounds are the second major component of crude oil, with asphalthenes, consisting of stacks of highly polymerized aromatic structures (average of 16 rings), completing the list of major oil hydrocarbon components. Also shown in Figure 1 are several important classes of compounds that are extensively used in "fingerprinting" crude oil or petroleum sources: sterols derived from steroid, hopanol derived from bacteriohopanetetrols, and pristane and phytane derived from phytol (from chlorophyll) during diagenesis.

Photocatalytic decomposition of carboxylated molecules on light-exposed martian regolith and its relation to methane production on Mars.

PubMed

Shkrob, Ilya A; Chemerisov, Sergey D; Marin, Timothy W

2010-05-01

We propose that the paucity of organic compounds in martian soil can be accounted for by efficient photocatalytic decomposition of carboxylated molecules due to the occurrence of the photo-Kolbe reaction at the surface of particulate iron(III) oxides that are abundant in the martian regolith. This photoreaction is initiated by the absorption of UVA light, and it readily occurs even at low temperature. The decarboxylation is observed for miscellaneous organic carboxylates, including the nonvolatile products of kerogen oxidation (that are currently thought to accumulate in the soil) as well as alpha-amino acids and peptides. Our study indicates that there may be no "safe haven" for these organic compounds on Mars; oxidation by reactive radicals, such as hydroxyl, is concerted with photocatalytic reactions on the oxide particles. Acting together, these two mechanisms result in mineralization of the organic component. The photooxidation of acetate (the terminal product of radical oxidation of the aliphatic component of kerogen) on the iron(III) oxides results in the formation of methane; this reaction may account for seasonably variable production of methane on Mars. The concomitant reduction of Fe(III) in the regolith leads to the formation of highly soluble ferrous ions that contribute to weathering of the soil particles.

Composition of dissolved organic matter in groundwater

NASA Astrophysics Data System (ADS)

Longnecker, Krista; Kujawinski, Elizabeth B.

2011-05-01

Groundwater constitutes a globally important source of freshwater for drinking water and other agricultural and industrial purposes, and is a prominent source of freshwater flowing into the coastal ocean. Therefore, understanding the chemical components of groundwater is relevant to both coastal and inland communities. We used electrospray ionization coupled with Fourier-transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS) to examine dissolved organic compounds in groundwater prior to and after passage through a sediment-filled column containing microorganisms. The data revealed that an unexpectedly high proportion of organic compounds contained nitrogen and sulfur, possibly due to transport of surface waters from septic systems and rain events. We matched 292 chemical features, based on measured mass:charge ( m/z) values, to compounds stored in the Kyoto Encyclopedia of Genes and Genomes (KEGG). A subset of these compounds (88) had only one structural isomer in KEGG, thus supporting tentative identification. Most identified elemental formulas were linked with metabolic pathways that produce polyketides or with secondary metabolites produced by plants. The presence of polyketides in groundwater is notable because of their anti-bacterial and anti-cancer properties. However, their relative abundance must be quantified with appropriate analyses to assess any implications for public health.

Chemical characterization of organic aerosol above a mid-latitude forest reveals a complex mixture of highly-functionalized chemical species and diverse structural features with temporal variability

NASA Astrophysics Data System (ADS)

Gentner, D. R.; Ditto, J.; Barnes, E.; Khare, P.

2017-12-01

Highly-functionalized organic compounds are known to be a major component of the complex mixture of the particle-phase compounds that comprise organic aerosol, yet little is known about the identity of many of these compounds, and their formation pathways and roles in atmospheric processes are poorly understood. We present results from the comprehensive chemical speciation of PM10 organic aerosols collected in July 2016 at the remote mid-latitude forest field site during PROPHET. Samples were analyzed via liquid and gas chromatography coupled with a quadrupole time-of-flight tandem mass spectrometry (MS×MS) following electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). 8 hr samples were collected during day- and night-time sampling periods rather than more typical 24-hour samples. This analysis of the organic aerosol yielded over 12,000 unique compounds for which we have high accuracy molecular masses, formulas, and additional information on structural features using MS×MS. O:C ratios were 0.3 on average, yet the top 10% of compounds ranged 0.7-2.3. 70% and 69% of day- and night-time samples were nitrogen-containing, whereas 26% and 24% contained sulfur, respectively. Within these broader molecular categories, we observed a wide variety of molecular features that reveal a diversity of functional groups and moieties. In this presentation, we present the results of our speciation, temporal variability, connections to air parcel back trajectories and other bulk properties, and potential formation pathways.

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.

Novel Reagents for Multi-Component Reactions

NASA Astrophysics Data System (ADS)

Wang, Yanguang; Basso, Andrea; Nenajdenko, Valentine G.; Gulevich, Anton V.; Krasavin, Mikhail; Bushkova, Ekaterina; Parchinsky, Vladislav; Banfi, Luca; Basso, Andrea; Cerulli, Valentina; Guanti, Giuseppe; Riva, Renata; Rozentsveig, Igor B.; Rozentsveig, Gulnur N.; Popov, Aleksandr V.; Serykh, Valeriy J.; Levkovskaya, Galina G.; Cao, Song; Shen, Li; Liu, Nianjin; Wu, Jingjing; Li, Lina; Qian, Xuhong; Chen, Xiaopeng; Wang, Hongbo; Feng, Jinwu; Wang, Yanguang; Lu, Ping; Heravi, Majid M.; Sadjadi, Samaheh; Kazemizadeh, Ali Reza; Ramazani, Ali; Kudyakova, Yulia S.; Goryaeva, Marina V.; Burgart, Yanina V.; Saloutin, Victor I.; Mossetti, Riccardo; Pirali, Tracey; Tron, Gian Cesare; Rozhkova, Yulia S.; Mayorova, Olga A.; Shklyaev, Yuriy V.; Zhdanko, Alexander G.; Nenajdenko, Valentine G.; Stryapunina, Olga G.; Plekhanova, Irina V.; Glushkov, Vladimir A.; Shklyaev, Yurii V.

Ketenimines are a class of versatile and highly reactive intermediates that can participate in a variety of organic reactions, such as nucleophilic additions, radical additions, [2 + 2] and [2 + 4] cycloadditions, and sigmatropic rearrangements. In this presentation, we report on a series of multi-component reactions that involve a ketenimine intermediate. These reactions could furnish diverse heterocyclic compounds, including functionalized iminocoumarin, iminodihydroqunolines, iminothiochromens, pyrrolines, isoquinolines, pyridines, β-lactams, imino-1,2-dihydrocoumarins, and benzimidazoles.

The Physical and Chemical Characterization of Ten Military Turbine Engine Lubricants.

DTIC Science & Technology

1979-09-01

fractions have been further evaluated by chemical hydrolysis and derivitized to determine the exact composition of the parent acid and alcohol components...separates the ester compounds into their original alcohol and acid components, This cleavage process produces the acid as a water—soluble salt which...allows the extraction and recovery of the alcohol from the acid salt by organic solvent extraction. In turn, the acid salt can be converted to the free

Separation process using pervaporation and dephlegmation

DOEpatents

Vane, Leland M.; Mairal, Anurag P.; Ng, Alvin; Alvarez, Franklin R.; Baker, Richard W.

2004-06-29

A process for treating liquids containing organic compounds and water. The process includes a pervaporation step in conjunction with a dephlegmation step to treat at least a portion of the permeate vapor from the pervaporation step. The process yields a membrane residue stream, a stream enriched in the more volatile component (usually the organic) as the overhead stream from the dephlegmator and a condensate stream enriched in the less volatile component (usually the water) as a bottoms stream from the dephlegmator. Any of these may be the principal product of the process. The membrane separation step may also be performed in the vapor phase, or by membrane distillation.

LEVOGLUCOSAN, A TRACER FOR CELLULOSE IN BIOMASS BURNING AND ATMOSPHERIC PARTICLES. (R823990)

EPA Science Inventory

Abstract

The major organic components of smoke particles from biomass burning are monosaccharide derivatives from the breakdown of cellulose, accompanied by generally lesser amounts of straight-chain, aliphatic and oxygenated compounds and terpenoids from vegetation wa...

40 CFR 59.103 - Container labeling requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 5 2010-07-01 2010-07-01 false Container labeling requirements. 59.103... National Volatile Organic Compound Emission Standards for Automobile Refinish Coatings § 59.103 Container... automobile refinish coating or coating component container or package, the day, month, and year on which the...

High Throughput Exposure Modeling of Semi-Volatile Chemicals in Articles of Commerce (SOT)

EPA Science Inventory

Chemical components of consumer products and articles of commerce such as carpet and clothing are key drivers of exposure in the near-field environment. These chemicals include semi-volatile organic compounds (SVOCs), some of which have been shown to alter endocrine functionality...

The Biological Potency Of Carbonaceous Nanoparticles Is Associated With The State Of Oxidation Of Surface Carbon Atoms

EPA Science Inventory

Epidemiological studies have shown that exposure to ambient particulate matter (PM) is associated with excess morbidity and mortality. An important component of PM consists of inorganic and organic compounds adsorbed onto a carbonaceous particle core. Toxicological studies indica...

Greening up Auto Part Manufacturing: A Collaboration between Academia and Industry

ERIC Educational Resources Information Center

Kneas, Kristi A.; Armstrong, Drew L.; Brank, Alice R.; Johnson, Amanda L.; Kissinger, Chelsea A.; Mabe, Adam R.; Sezer, Ozge; Fontinell, Mike

2009-01-01

Historically, manufacture of automotive electronic components and screen-printing of automotive instrument clusters at DENSO Manufacturing Tennessee, Inc. required washing of equipment such as screens, stencils, and jigs with sizable quantities of volatile organic compounds and hazardous air pollutants. Collaborative efforts between the Maryville…

Superfund Innovative Technology Evaluation - Demonstration Bulletin: In-Situ Soil Stabilization

EPA Science Inventory

In-situ stabilization technology immobilizes organics and inorganic compounds in wet or dry soils by using reagents (additives) to polymerize with the soils and sludges producing a cement-like mass. Two basic components of this technology are the Geo-Con/DSM Deep Soil Mixing Sy...

GREENER CHEMICAL SYNTHESES VIA MECHANOCHEMICAL MIXING OR USING MICROWAVE IRRADIATION IN ECO-FRIENDLY MEDIA

EPA Science Inventory

A simple approach to rapid organic synthesis or transformation using ‘greener’ reaction conditions, especially in the context of multi-component condensation reactions that are amenable to building of libraries of compounds, is very desirable. A variety of eco-friendly reactions ...

77 FR 47536 - Revisions to the California State Implementation Plan, Mojave Desert, Northern Sierra, Sacramento...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-08-09

... volatile organic compound (VOC) emissions from automotive parts and component, automobile refinishing... metal parts and products, miscellaneous uses, automobile refinishing processes and automotive equipment... Techniques Guidelines for Automobile and Light-Duty Truck Assembly Coatings,'' EPA (EPA-453/R-08-006...

Self-Assembling Amphiphilic Molecules: A Possible Relationship Between Interstellar Chemistry and Meteoritic Organics

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Dworkin, Jason P.; Deamer, David W.; Allamandola, Louis J.; DeVincenzi, Donald (Technical Monitor)

2001-01-01

Interstellar gas and dust comprise the primary material from which the solar system formed. Evidence that some of this material was organic in nature and survived incorporation into the protosolar nebula is provided by the presence of deuterium-enriched organics in meteorites and interplanetary dust particles. Once the inner planets had sufficiently cooled, late accretionary infall of meteoroids and cosmic dust must have seeded them with some of these complex organic compounds. Delivery of such extraterrestrial compounds may have contributed to the organic inventory necessary for the origin of life. Interstellar ices, the building blocks of comets, tie up a large fraction of the biogenic elements available in molecular clouds. In our efforts to understand their synthesis, chemical composition, and physical properties, we report here that a complex mixture of molecules is produced by ultraviolet (UV) photolysis of realistic, interstellar ice analogs, and that some of the components have properties relevant to the origin of life, including the ability to self-assemble into vesicular structures.

Electrocatalytic hydrogenation and hydrodeoxygenation of oxygenated and unsaturated organic compounds

DOEpatents

Jackson, James E.; Lam, Chun Ho; Saffron, Christopher M.; Miller, Dennis J.

2018-04-24

A process and related electrode composition are disclosed for the electrocatalytic hydrogenation and/or hydrodeoxygenation of organic substrates such as biomass-derived bio-oil components by the production of hydrogen atoms on a catalyst surface followed by the reaction of the hydrogen atoms with the organic reactants. Biomass fast pyrolysis-derived bio-oil is a liquid mixture containing hundreds of organic compounds with chemical functionalities that are corrosive to container materials and are prone to polymerization. A high surface area skeletal metal catalyst material such as Raney Nickel can be used as the cathode. Electrocatalytic hydrogenation and/or hydrodeoxygenation convert the organic substrates under mild conditions to reduce coke formation and catalyst deactivation. The process converts oxygen-containing functionalities and unsaturated bonds into chemically reduced forms with an increased hydrogen content. The process is operated at mild conditions, which enables it to be a good means for stabilizing bio-oil to a form that can be stored and transported using metal containers and pipes.

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

PubMed

Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

2016-08-15

A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

Air-to-sea fluxes of lipids at Enewetak Atoll

NASA Astrophysics Data System (ADS)

Zafiriou, Oliver C.; Gagosian, Robert B.; Peltzer, Edward T.; Alford, Jane B.; Loder, T.

1985-02-01

We report data for the Enewetak site of the SEAREX program from the rainy season in 1979. The concentrations of n-alkanes, n-alkanols, sterols, n-alkanoic acids and their salts, and total organic compounds in rain are reported, as well as the apparent gaseous hydrocarbon concentrations. These data and information on the particulate forms are analyzed in conjunction with ancillary chemical and meteorological data to draw inferences about sources, fluxes, and chemical speciations. While the higher molecular weight lipid biomarker components are exclusively terrestrial, the organic carbon in rain may be derived from atmospheric transformations of terrestrial carbon. Distinctively marine components are nearly absent. Comparison of the scavenging ratios of the organic components in rain vs. those for clays reveals that the alkanoic acids and the higher molecular weight alkanols behave as essentially particulate materials, whereas lower alkanols and most hydrocarbons show much higher scavenging ratios, probably due to the involvement of a gaseous phase or sampling artifact. Vaporization in the atmosphere and scavenging of a gas phase would lead to higher scavenging ratios; vaporization during sampling would give low aerosol concentrations and high gas-phase concentrations, leading to high scavenging ratios. The major fluxes at Enewetak result from rain rather than dry deposition, and extrapolating the measured values to meaningful annual averages requires adjustment for seasonally varying source intensity and rain dynamics. Aerosol data for other seasons and other substances are used to correct for source-strength intensity variations, and a 210Pb/organic compound correlation is established and extrapolated to adjust for rainfall volume effects. These corrections, assumed independent and applied together, yield inferred fluxes 2.5-9 times larger than the fluxes calculated for mean concentrations. The inferred fluxes to the ocean, while small compared to primary production, are large enough to have potential impacts in the cycle of dissolved organic carbon and the sedimentary geochemistry of refractory lipid components.

Mediated electrochemical oxidation of organic wastes using a Co (III) mediator in a nitric acid based system

DOEpatents

Balazs, G.B.; Chiba, Z.; Lewis, P.R.; Nelson, N.; Steward, G.A.

1999-06-15

An electrochemical cell with a Co(III) mediator and nitric acid electrolyte provides efficient destruction of organic and mixed wastes. The organic waste is concentrated in the anolyte reservoir, where the mediator oxidizes the organics and insoluble transuranic compounds and is regenerated at the anode until the organics are converted to CO[sub 2]. The nitric acid is an excellent oxidant that facilitates the destruction of the organic components. The anode is not readily attacked by the nitric acid solution, thus the cell can be used for extended continual operation without electrode replacement. 2 figs.

Organic Wastewater Compounds, Pharmaceuticals, andColiphage in Ground Water Receiving Discharge from OnsiteWastewater Treatment Systems near La Pine, Oregon:Occurrence and Implications for Transport

USGS Publications Warehouse

Hinkle, Stephen J.; Weick, Rodney J.; Johnson, Jill M.; Cahill, Jeffery D.; Smith, Steven G.; Rich, Barbara J.

2005-01-01

The occurrence of organic wastewater compounds (components of 'personal care products' and other common household chemicals), pharmaceuticals (human prescription and nonprescription medical drugs), and coliphage (viruses that infect coliform bacteria, and found in high concentrations in municipal wastewater) in onsite wastewater (septic tank effluent) and in a shallow, unconfined, sandy aquifer that serves as the primary source of drinking water for most residents near La Pine, Oregon, was documented. Samples from two types of observation networks provided basic occurrence data for onsite wastewater and downgradient ground water. One observation network was a group of 28 traditional and innovative (advanced treatment) onsite wastewater treatment systems and associated downgradient drainfield monitoring wells, referred to as the 'innovative systems network'. The drainfield monitoring wells were located adjacent to or under onsite wastewater treatment system drainfield lines. Another observation network, termed the 'transect network', consisted of 31 wells distributed among three transects of temporary, stainless-steel-screened, direct-push monitoring wells installed along three plumes of onsite wastewater. The transect network, by virtue of its design, also provided a basis for increased understanding of the transport of analytes in natural systems. Coliphage were frequently detected in onsite wastewater. Coliphage concentrations in onsite wastewater were highly variable, ranging from less than 1 to 3,000,000 plaque forming units per 100 milliliters. Coliphage were occasionally detected (eight occurrences) at low concentrations in samples from wells located downgradient from onsite wastewater treatment system drainfield lines. However, coliphage concentrations were below method detection limits in replicate or repeat samples collected from the eight sites. The consistent absence of coliphage detections in the replicate or repeat samples is interpreted to indicate that the detections reported for ground-water samples represented low-level field or laboratory contamination, and it would appear that coliphage were effectively attenuated to less than 1 PFU/100 mL over distances of several feet of transport in the La Pine aquifer and (or) overlying unsaturated zone. Organic wastewater compounds were frequently detected in onsite wastewater. Of the 63 organic wastewater compounds in the analytical schedule, 45 were detected in the 21 samples of onsite wastewater. Concentrations of organic wastewater compounds reached a maximum of 1,300 ug/L (p-cresol). Caffeine was detected at concentrations as high as 320 ug/L. Fourteen of the 45 compounds were detected in more than 90 percent of onsite wastewater samples. Fewer (nine) organic wastewater compounds were detected in ground water, despite the presence of nitrate and chloride likely from onsite wastewater sources. The nine organic wastewater compounds that were detected in ground-water samples were acetyl-hexamethyl-tetrahydro-naphthalene (AHTN), caffeine, cholesterol, hexahydrohexamethyl-cyclopentabenzopyran, N,N-diethyl-meta-toluamide (DEET), tetrachloroethene, tris (2-chloroethyl) phosphate, tris (dichloroisopropyl) phosphate, and tributyl phosphate. Frequent detection of household-chemical type organic wastewater compounds in onsite wastewater provides evidence that some of these organic wastewater compounds may be useful indicators of human waste effluent dispersal in some hydrologic environments. The occurrence of organic wastewater compounds in ground water downgradient from onsite wastewater treatment systems demonstrates that a subgroup of organic wastewater compounds is transported in the La Pine aquifer. The consistently low concentrations (generally less than 1 ug/L) of organic wastewater compounds in water samples collected from wells located no more than 19 feet from drainfield lines indicates that the reactivity (sorption, degradation) of this suite of organic waste

Chemical aging of single and multicomponent biomass burning aerosol surrogate-particles by OH: Implications for cloud condensation nucleus activity

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

Thalman, R.; Thalman, R.; Wang, J.

Multiphase OH and O₃ oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low soluble single-component OA by OH and O₃ can increase their water-solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water-solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate-particles exposed to OH andmore » O₃ is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH/O₃ exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O₃ exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~0.1, indicating that chemically-aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally-mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH exposed MNC-coated KS particles is similar to the OH unexposed atomized 1:1 by mass MNC: KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical aging has no significant impact on OA hygroscopicity. The organic compounds exhibiting low solubility behave as if they are infinitely soluble when mixed with a sufficient amount of water-soluble compounds. At and beyond this point, the particles' CCN activity is governed entirely by the water-soluble fraction and not influenced by the oxidized organic fraction. Our results have important implications for heterogeneous oxidation and its impact on cloud formation given that atmospheric aerosol is a complex mixture of organic and inorganic compounds exhibiting a wide-range of solubilities.« less

Chemical aging of single and multicomponent biomass burning aerosol surrogate particles by OH: implications for cloud condensation nucleus activity

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

Slade, J. H.; Thalman, R.; Wang, J.

Multiphase OH and O 3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low-soluble single-component OA by OH and O 3 can increase their water solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate particlesmore » exposed to OH and O 3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH and O 3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O 3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~ 0.1, indicating that chemically aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH-exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical aging has no significant impact on OA hygroscopicity. The organic compounds exhibiting low solubility behave as if they are infinitely soluble when mixed with a sufficient number of water-soluble compounds. At and beyond this point, the particles' CCN activity is governed entirely by the water-soluble fraction and is not influenced by the oxidized organic fraction. Our results have important implications for heterogeneous oxidation and its impact on cloud formation given that atmospheric aerosol is a complex mixture of organic and inorganic compounds exhibiting a wide range of solubilities.« less

Chemical aging of single and multicomponent biomass burning aerosol surrogate particles by OH: implications for cloud condensation nucleus activity

DOE PAGES

Slade, J. H.; Thalman, R.; Wang, J.; ...

2015-09-14

Multiphase OH and O 3 oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low-soluble single-component OA by OH and O 3 can increase their water solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate particlesmore » exposed to OH and O 3 is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH and O 3 exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O 3 exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~ 0.1, indicating that chemically aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH-exposed MNC-coated KS particles is similar to the OH unexposed atomized 1 : 1 by mass MNC : KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical aging has no significant impact on OA hygroscopicity. The organic compounds exhibiting low solubility behave as if they are infinitely soluble when mixed with a sufficient number of water-soluble compounds. At and beyond this point, the particles' CCN activity is governed entirely by the water-soluble fraction and is not influenced by the oxidized organic fraction. Our results have important implications for heterogeneous oxidation and its impact on cloud formation given that atmospheric aerosol is a complex mixture of organic and inorganic compounds exhibiting a wide range of solubilities.« less

Chemical aging of single and multicomponent biomass burning aerosol surrogate-particles by OH: Implications for cloud condensation nucleus activity

DOE PAGES

Thalman, R.; Thalman, R.; Wang, J.; ...

2015-03-06

Multiphase OH and O₃ oxidation reactions with atmospheric organic aerosol (OA) can influence particle physicochemical properties including composition, morphology, and lifetime. Chemical aging of initially insoluble or low soluble single-component OA by OH and O₃ can increase their water-solubility and hygroscopicity, making them more active as cloud condensation nuclei (CCN) and susceptible to wet deposition. However, an outstanding problem is whether the effects of chemical aging on their CCN activity are preserved when mixed with other organic or inorganic compounds exhibiting greater water-solubility. In this work, the CCN activity of laboratory-generated biomass burning aerosol (BBA) surrogate-particles exposed to OH andmore » O₃ is evaluated by determining the hygroscopicity parameter, κ, as a function of particle type, mixing state, and OH/O₃ exposure applying a CCN counter (CCNc) coupled to an aerosol flow reactor (AFR). Levoglucosan (LEV), 4-methyl-5-nitrocatechol (MNC), and potassium sulfate (KS) serve as representative BBA compounds that exhibit different hygroscopicity, water solubility, chemical functionalities, and reactivity with OH radicals, and thus exemplify the complexity of mixed inorganic/organic aerosol in the atmosphere. The CCN activities of all of the particles were unaffected by O₃ exposure. Following exposure to OH, κ of MNC was enhanced by an order of magnitude, from 0.009 to ~0.1, indicating that chemically-aged MNC particles are better CCN and more prone to wet deposition than pure MNC particles. No significant enhancement in κ was observed for pure LEV particles following OH exposure. κ of the internally-mixed particles was not affected by OH oxidation. Furthermore, the CCN activity of OH exposed MNC-coated KS particles is similar to the OH unexposed atomized 1:1 by mass MNC: KS binary-component particles. Our results strongly suggest that when OA is dominated by water-soluble organic carbon (WSOC) or inorganic ions, chemical aging has no significant impact on OA hygroscopicity. The organic compounds exhibiting low solubility behave as if they are infinitely soluble when mixed with a sufficient amount of water-soluble compounds. At and beyond this point, the particles' CCN activity is governed entirely by the water-soluble fraction and not influenced by the oxidized organic fraction. Our results have important implications for heterogeneous oxidation and its impact on cloud formation given that atmospheric aerosol is a complex mixture of organic and inorganic compounds exhibiting a wide-range of solubilities.« less

A target and nontarget strategy for identification or characterization of the chemical ingredients in Chinese herb preparation Shuang-Huang-Lian oral liquid by ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry.

PubMed

Zhang, Feng-Xiang; Li, Min; Yao, Zhi-Hong; Li, Chang; Qiao, Li-Rui; Shen, Xiu-Yu; Yu, Kate; Dai, Yi; Yao, Xin-Sheng

2018-03-01

A target and nontarget strategy based on in-house chemical components library was developed for rapid and comprehensive analysis of complicated components from traditional Chinese medicine preparation Shuang-Huang-Lian oral liquid. The sample was analyzed by ultra-performance liquid chromatography-quadrupole time-of-flight mass spectrometry using generic acquisition parameters. Automated detection and data filtering were performed on the UNIFI™ software and the detected peaks were evaluated against an in-house library. As a result, a total of 170 chemical components (110 target compounds and 60 nontarget ones) were identified or tentatively characterized, including 54 flavonoids, 30 phenylethanoid glycosides, 16 iridoid glycosides, 14 lignans, 32 organic acids, 19 triterpenoid saponins and five other types of compounds. Among them, 44 compounds were further confirmed by comparison with reference standards. It was demonstrated that this systematical approach could be successfully applied for rapid identification of multiple compounds in traditional Chinese medicine and its preparations. Furthermore, this work established the foundation for the further investigation on the metabolic fates of multiple ingredients in Shuang-Huang-Lian oral liquid. Copyright © 2017 John Wiley & Sons, Ltd.

Air-to-sea fluxes of lipids at enewetak atoll

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

Zafiriou, O.C.; Gagosian, R.B.; Peltzer, E.T.

1985-02-20

We report data for the Enewetak site of the SEAREX program from the rainy season in 1979. The concentrations of n-alkanes, n-alkanols, sterols, n-alkanoic acids and their salts, and total organic compounds in rain are reported, as well as the apparent gaseous hydrocarbon concentrations. These data and information on the particulate forms are analyzed in conjunction with ancillary chemical and meterological data to draw inferences about sources, fluxes, and chemical speciations. While the higher molecular weight lipid biomarker components are exclusively terrestrial, the organic carbon in rain may be derived from atmospheric transformations of terrestrial carbon. Distinctively marine components aremore » nearly absent. Comparison of the scavenging ratios of the organic components in rain vs. those for clays reveals that the alkanoic acids and the higher molecular weight alkanols behave as essentially particulate materials, whereas lower alkanols and most hydrocarbons show much higher scavenging ratios, probably due to the involvement of a gaseous phase or sampling artifact. Vaporization in the atmosphere and scaveging of a gas phase would lead to higher scaveging ratios; vaporization during sampling would give low aerosol concentrations and high gas-phase concentrations, leading to high scavening ratios. The major fluxes at Enewetak result from rain rather than dry deposition, and extrapolating the measured values to meaningful annual averages requires adjustment for seasonally varying source intensity and rain dynamics. Aerosol data for other seasons and other substances are used to correct for source-strength intensity variations, and a /sup 210/Pb/organic compound correlation is established and extrapolated to adjust for rainfall volume effects.« less

Characterization of selected municipal solid waste components to estimate their biodegradability.

PubMed

Bayard, R; Benbelkacem, H; Gourdon, R; Buffière, P

2018-06-15

Biological treatments of Residual Municipal Solid Waste (RMSW) allow to divert biodegradable materials from landfilling and recover valuable alternative resources. The biodegradability of the waste components needs however to be assessed in order to design the bioprocesses properly. The present study investigated complementary approaches to aerobic and anaerobic biotests for a more rapid evaluation. A representative sample of residual MSW was collected from a Mechanical Biological Treatment (MBT) plant and sorted out into 13 fractions according to the French standard procedure MODECOM™. The different fractions were analyzed for organic matter content, leaching behavior, contents in biochemical constituents (determined by Van Soest's acid detergent fiber method), Biochemical Oxygen Demand (BOD) and Bio-Methane Potential (BMP). Experimental data were statistically treated by Principal Components Analysis (PCA). Cumulative oxygen consumption from BOD tests and cumulative methane production from BMP tests were found to be positively correlated in all waste fractions. No correlation was observed between the results from BOD or BMP bioassays and the contents in cellulose-like, hemicelluloses-like or labile organic compounds. No correlation was observed either with the results from leaching tests (Soluble COD). The contents in lignin-like compounds, evaluated as the non-extracted RES fraction in Van Soest's method, was found however to impact negatively the biodegradability assessed by BOD or BMP tests. Since cellulose, hemicelluloses and lignin are the polymers responsible for the structuration of lignocellulosic complexes, it was concluded that the structural organization of the organic matter in the different waste fractions was more determinant on biodegradability than the respective contents in individual biopolymers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Simultaneous flame ionization and absorbance detection of volatile and nonvolatile compounds by reversed-phase liquid chromatography with a water mobile phase.

PubMed

Bruckner, C A; Ecker, S T; Synovec, R E

1997-09-01

A flame ionization detector (FID) is used to detect volatile organic compounds that have been separated by water-only reversed-phase liquid chromatography (WRP-LC). The mobile phase is 100% water at room temperature, without use of organic solvent modifiers. An interface between the LC and detector is presented, whereby a helium stream samples the vapor of volatile components from individual drops of the LC eluent, and the vapor-enriched gas stream is sent to the FID. The design of the drop headspace cell is simple because the water-only nature of the LC separation obviates the need to do any organic solvent removal prior to gas phase detection. Despite the absence of organic modifier, hydrophobic compounds can be separated in a reasonable time due to the low phase volume ratio of the WRP-LC columns. The drop headspace interface easily handles LC flows of 1 mL/min, and, in fact, compound detection limits are improved at faster liquid flow rates. The transfer efficiency of the headspace interface was estimated at 10% for toluene in water at 1 mL/min but varies depending on the volatility of each analyte. The detection system is linear over more than 5 orders of 1-butanol concentration in water and is able to detect sub-ppb amounts of o-xylene and other aromatic compounds in water. In order to analyze volatile and nonvolatile analytes simultaneously, the FID is coupled in series to a WRP-LC system with UV absorbance detection. WRP-LC improves UV absorbance detection limits because the absence of organic modifier allows the detector to be operated in the short-wavelength UV region, where analytes generally have significantly larger molar absorptivities. The selectivity the headspace interface provides for flame ionization detection of volatiles is demonstrated with a separation of 1-butanol, 1,1,2-trichloroethane (TCE), and chlorobenzene in a mixture of benzoic acid in water. Despite coelution of butanol and TCE with the benzoate anion, the nonvolatile benzoate anion does not appear in the FID signal, allowing the analytes of interest to be readily detected. The complementary selectivity of UV-visible absorbance detection and this implementation of flame ionization detection allows for the analysis of volatile and nonvolatile components of complex samples using WRP-LC without the requirement that all the components of interest be fully resolved, thus simplifying the sample preparation and chromatographic requirements. This instrument should be applicable to routine automated water monitoring, in which repetitive injection of water samples onto a gas chromatograph is not recommended.

High Performance Liquid Chromatography

NASA Astrophysics Data System (ADS)

Talcott, Stephen

High performance liquid chromatography (HPLC) has many applications in food chemistry. Food components that have been analyzed with HPLC include organic acids, vitamins, amino acids, sugars, nitrosamines, certain pesticides, metabolites, fatty acids, aflatoxins, pigments, and certain food additives. Unlike gas chromatography, it is not necessary for the compound being analyzed to be volatile. It is necessary, however, for the compounds to have some solubility in the mobile phase. It is important that the solubilized samples for injection be free from all particulate matter, so centrifugation and filtration are common procedures. Also, solid-phase extraction is used commonly in sample preparation to remove interfering compounds from the sample matrix prior to HPLC analysis.

The Geology of Liberia: A Selected Bibliography of Liberian Geology, Geography and Earth Science

DTIC Science & Technology

2006-05-01

acerca do Sistema do Oendolongo e da Serie do Sansicua ( Sistema do Congo Ocidental).” Translated title: “The marked orogenesis in the Cariango region...Nitrogen ratio; Chemistry, organic compounds; Chemistry, sediment; Components, terrigeneous; d13C Corg; delta 13C, organic carbon; Dinost/ TOC ...for Geosciences, Christian Albrechts University, Kiel; Isotopes, stable, general; Ketone/ TOC ; M6/5; M65; Mass spectrometer Finnigan MAT 251; Meteor

[Characteristics of odors and VOCs from sludge direct drying process].

PubMed

Chen, Wen-He; Deng, Ming-Jia; Luo, Hui; Zhang, Jing-Ying; Ding, Wen-Jie; Liu, Jun-Xin; Liu, Jun-Xin

2014-08-01

Co-processing sewage sludge by using the high-temperature feature of cement kiln can realize harmless disposal and energy recycling. In this paper, investigation on characteristics of the flue gas from sludge drying process was carried out in Guangzhou Heidelberg Yuexiu Cement Co., LTD. The composition and the main source of odors and volatile organic compounds (VOCs) emitted during the drying process were analyzed, aimed to provide scientific basis for the treatment of sewage sludge. Results showed that there were a large number of malodorous substances and VOCs in the flue gas. Sulfur dioxide and other sulfur-containing compounds were the main components in the malodorous substances, while benzene derivatives were predominant in VOCs. The compositions of odors and VOCs were influenced by the characteristics of the sludge and the heat medium (kiln tail gas). Total organic compounds in the sludge were significantly decreased after drying. Other organic substances such as volatile fatty acid, protein, and polysaccharide were also obviously reduced. The organic matter in sludge was the main source of VOCs in the flue gas. Part of sulfurous substances, such as sulfur dioxide, carbon disulfide, were from sulfur-containing substances in the sludge, and the rest were from the kiln tail gas itself.

Release of non-methane organic compounds during simulated landfilling of aerobically pretreated municipal solid waste.

PubMed

Zhang, Yuanyuan; Yue, Dongbei; Liu, Jianguo; Lu, Peng; Wang, Ying; Liu, Jing; Nie, Yongfeng

2012-06-30

Characteristics of non-methane organic compounds (NMOCs) emissions during the anaerobic decomposition of untreated (APD-0) and four aerobically pretreated (APD-20, APD-39, APD-49, and APD-63) samples of municipal solid waste (MSW) were investigated in laboratory. The cumulative mass of the NMOCs of APD-20, APD-39, APD-49, and APD-63 accounted for 15%, 9%, 16%, and 15% of that of APD-0, respectively. The intensities of the NMOC emissions calculated by dividing the cumulative NMOC emissions by the quantities of organic matter removed (Q(VS)) decreased from 4.1 mg/kg Q(VS) for APD-0 to 0.8-3.4 mg/kg Q(VS) for aerobically pretreated MSW. The lipid and starch contents might have significant impact on the intensity of the NMOC emissions. Alkanes dominated the NMOCs released from the aerobically pretreated MSW, while oxygenated compounds were the chief component of the NMOCs generated from untreated MSW. Aerobic pretreatment of MSW prior to landfilling reduces the organic content of the waste and the intensity of the NMOC emissions, and increases the odor threshold, thereby reducing the environmental impact of landfills. Copyright © 2012 Elsevier Ltd. All rights reserved.

Radial Chromatography for the Separation of Nitroaniline Isomers

ERIC Educational Resources Information Center

Miller, Robert B.; Case, William S.

2011-01-01

Separation techniques are usually presented in the undergraduate organic laboratory to teach students how to purify and isolate compounds. Often the concept of liquid chromatography is introduced by having students create "silica gel columns" to separate components of a reaction mixture. Although useful, column chromatography can be a laborious…

CLEANER SYNTHESIS OF ORGANIC COMPOUNDS USING SEMICONDUCTER PHOTOCATALYSIS

EPA Science Inventory

The chemical industry is a significant component of the domestic economy, generating well over $250 billion in sales and a trade surplus exceeding $15 billion in each of the last 5 years. The industry is also a major source of industrial waste and is the dominant source of hazard...

EXPOSURE TO PARTICULATE MATTER, VOLATILE ORGANIC COMPOUNDS, AND OTHER AIR POLLUTANTS INSIDE PATROL CARS

EPA Science Inventory

People driving in a vehicle might receive an enhanced dose of mobile source pollutants that are considered a potential risk for cardiovascular diseases. The exposure to components of air pollution in highway patrol vehicles, at an ambient, and a roadside location was determined d...

Improving the knowledge on Piper betle: targeted metabolite analysis and effect on acetylcholinesterase.

PubMed

Valentão, Patrícia; Gonçalves, Rui F; Belo, Cristóvão; de Pinho, Paula Guedes; Andrade, Paula B; Ferreres, Federico

2010-10-01

Piper betle is a species growing in South East Asia, where its leaves are economically and medicinally important. To screen the highest possible number of volatile and semivolatile components, the leaves were subjected to headspace solid-phase microextraction, hydrodistillation and Soxhlet extraction, prior to analysis by GC/MS. Fifty compounds (identified by comparison with standard compounds or tentatively by National Institute of Standards and Technology database) were determined, 23 being described for the first time in this matrix. An aqueous extract was also analysed, in which only seven compounds were characterized. The organic acids' composition of this extract was determined by HPLC/UV and eight compounds are reported for the first time in P. betle. This extract also displayed acetylcholinesterase inhibitory capacity.

QSAR models for degradation of organic pollutants in ozonation process under acidic condition.

PubMed

Zhu, Huicen; Guo, Weimin; Shen, Zhemin; Tang, Qingli; Ji, Wenchao; Jia, Lijuan

2015-01-01

Although some researches about the degradation of organic pollutants have been carried out during recent years, reaction rate constants are available only for homologue compounds with similar structures or components. Therefore, it is of great significance to find a universal relationship between reaction rate and certain parameters of several diverse organic pollutants. In this study, removal ratio and kinetics of 33 kinds of organic substances were investigated by ozonation process, including azo dyes, heterocyclic compounds, ionic compounds and so on. Most quantum chemical parameters were conducted by using Gaussian 09 at the DFT B3LYP/6-311G level, including μ, q H(+), q(C)minq(C)max, ELUMO and EHOMO. Other descriptors, bond order (BO) as well as Fukui indices (f(+), f(-) and f(0)), were calculated by Material Studio 6.1 at Dmol(3)/GGA-BLYP/DNP(3.5) basis for each organic compound. The recommended model for predicting rate constants was lnk'=1.978-95.484f(0)x-3.350q(C)min+38.221f(+)x, which had the squared regression coefficient R(2)=0.763 and standard deviation SD=0.716. The results of t test and the Fisher test suggested that the model exhibited optimum stability. Also, the model was validated by internal and external validations. Recommended QSAR model showed that the highest f(0) value of main-chain carbons (f(0)x) is more closely related to lnk' than other quantum descriptors. Copyright © 2014 Elsevier Ltd. All rights reserved.

Low molecular weight components in an aquatic humic substance as characterized by membrane dialysis and orbitrap mass spectrometry.

PubMed

Remucal, Christina K; Cory, Rose M; Sander, Michael; McNeill, Kristopher

2012-09-04

Suwannee River fulvic acid (SRFA) was dialyzed through a 100-500 molecular weight cutoff dialysis membrane, and the dialysate and retentate were analyzed by UV-visible absorption and high-resolution Orbitrap mass spectrometry (MS). A significant fraction (36% based on dissolved organic carbon) of SRFA passed through the dialysis membrane. The fraction of SRFA in the dialysate had a different UV-visible absorption spectrum and was enriched in low molecular weight molecules with a more aliphatic composition relative to the initial SRFA solution. Comparison of the SRFA spectra collected by Orbitrap MS and Fourier transform ion cyclotron resonance MS (FT-ICR MS) demonstrated that the mass accuracy of the Orbitrap MS is sufficient for determination of unique molecular formulas of compounds with masses <600 Da in a complex mixture, such as SRFA. The most intense masses detected by Orbitrap MS were found in the 100-200 Da mass range. Many of these low molecular masses corresponded to molecular formulas of previously identified compounds in organic matter, lignin, and plants, and the use of the standard addition method provided an upper concentration estimate of selected target compounds in SRFA. Collectively, these results provide evidence that SRFA contains low molecular weight components that are present individually or in loosely bound assemblies.

[Quality evaluation of Artemisiae Argyi Folium based on fingerprint analysis and quantitative analysis of multicomponents].

PubMed

Guo, Long; Jiao, Qian; Zhang, Dan; Liu, Ai-Peng; Wang, Qian; Zheng, Yu-Guang

2018-03-01

Artemisiae Argyi Folium, the dried leaves of Artemisia argyi, has been widely used in traditional Chinese and folk medicines for treatment of hemorrhage, pain, and skin itch. Phytochemical studies indicated that volatile oil, organic acid and flavonoids were the main bioactive components in Artemisiae Argyi Folium. Compared to the volatile compounds, the research of nonvolatile compounds in Artemisiae Argyi Folium are limited. In the present study, an accurate and reliable fingerprint approach was developed using HPLC for quality control of Artemisiae Argyi Folium. A total of 10 common peaks were marked，and the similarity of all the Artemisiae Argyi Folium samples was above 0.940. The established fingerprint method could be used for quality control of Artemisiae Argyi Folium. Furthermore, an HPLC method was applied for simultaneous determination of seven bioactive compounds including five organic acids and two flavonoids in Artemisiae Argyi Folium and Artemisiae Lavandulaefoliae Folium samples. Moreover, chemometrics methods such as hierarchical clustering analysis and principal component analysis were performed to compare and discriminate the Artemisiae Argyi Folium and Artemisiae Lavandulaefoliae Folium based on the quantitative data of analytes. The results indicated that simultaneous quantification of multicomponents coupled with chemometrics analysis could be a well-acceptable strategy to identify and evaluate the quality of Artemisiae Argyi Folium. Copyright© by the Chinese Pharmaceutical Association.

Vapor space characterization of Waste Tank 241-TY-104 (in situ): Results from samples collected on 8/5/94

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

Ligotke, M.W.; Pool, K.H.; Lucke, R.B.

1995-10-01

This report describes inorganic and organic analyses results from in situ samples obtained from the headspace of the Hanford waste storage Tank 241-TY-104 (referred to as Tank TY-104). The results described here were obtained to support safety and toxicological evaluations. A summary of the results for inorganic and organic analytes is listed in Table 1. Detailed descriptions of the results appear in the text. Quantitative results were obtained for the inorganic compounds ammonia (NH{sub 3}), nitrogen dioxide (NO{sub 2}), nitric oxide (NO), and water (H{sub 2}O). Sampling for hydrogen cyanide (HCN) and sulfur oxides (SO{sub x}) was not performed. Inmore » addition, the authors looked for the 39 TO-14 compounds plus an additional 14 analytes. Of these, eight were observed above the 5-ppbv reporting cutoff. Twenty-four organic tentatively identified compounds (TICs) were observed above the reporting cutoff of (ca.) 10 ppbv and are reported with concentrations that are semiquantitative estimates based on internal standard response factors. The 10 organic analytes with the highest estimated concentrations are listed in Table 1 and account for approximately 86% of the total organic components in Tank TY-104. Tank TY-104 is on the Ferrocyanide Watch List.« less

Sources of organic compounds in fine soil and sand particles during winter in the metropolitan area of Riyadh, Saudi Arabia.

PubMed

Rushdi, Ahmed I; Al-Mutlaq, Khalid; Simoneit, Bernd R T

2005-11-01

Major advances have been made in molecular marker analysis to distinguish between natural and anthropogenic organic matter inputs to the atmosphere. Resuspension of soil and sand by wind is one of the major mechanisms that produces particle dusts in the atmosphere. Soil and sand samples from the Riyadh area were collected in winter 2002, sieved to remove coarse particles and extracted with a mixture of dichloromethane and methanol (3:1, v:v). The total extracts were analyzed by gas chromatography-mass spectrometry in order to characterize the contents and identify the potential sources of the organic components. The major organic compounds of these extracts were derived from natural biogenic and anthropogenic sources. Organic compounds from natural sources, mainly vegetation, were major in samples from outside the city of Riyadh and included n-alkanes, n-alkanoic acids, n- alkanols, methyl alkanoates, and sterols. Anthropogenic inputs were significant in the fine particles of soil and sand samples collected from populated areas of the city. They consisted mainly of n-alkanes, hopanes, UCM (from vehicular emissions), and plasticizers (from discarded plastics, e.g., shopping bags). Carbohydrates had high concentrations in all samples and indicate sources from decomposed cellulose fibers and/or the presence of viable microbiota such as bacteria and fungi.

Distribution of volatile organic compounds over a semiconductor Industrial Park in Taiwan.

PubMed

Chiu, Kong-Hwa; Wu, Ben-Zen; Chang, Chih-Chung; Sree, Usha; Lo, Jiunn-Guang

2005-02-15

This study examined volatile organic compounds (VOC) concentration in ambient air collected during the years 2000--2003 at several different locations of Hsinchu Science-based Industrial Park (HSIP) in Taiwan. A canister automated GC-MS system analyzed the volatile organics in ambient air grasp samples according to T0-15 method. Oxygenated volatiles were the most abundant VOC detected in HSIP followed by aromatics that are commonly used as solvents in the semiconductor industries. The major components measured in the ambient air are 2-propanol (29-135 ppbv), acetone (12-164 ppbv), benzene (0.7-1.7 ppbv), and toluene (13-20 ppbv). At some of the sampling locations, odorous compounds such as carbon disulfide and dimethyl sulfide levels exceed threshold values. The estimated toluene/benzene ratio is very high at most of the sites. However, the total amount of VOC is reduced over the years from 2000 to 2003 due to strict implementation on use and discharge of solvents in industries. There exists no definite seasonal pattern for sporadic occurrence of high levels of some of the volatile organics. Stagnant weather conditions with low wind speeds aid accumulation of toxic species at ground level. The results entail that hi-tech semiconductor industries are still a potential source for harmful organic substances to surrounding microenvironment.

Organic-based molecular switches for molecular electronics.

PubMed

Fuentes, Noelia; Martín-Lasanta, Ana; Alvarez de Cienfuegos, Luis; Ribagorda, Maria; Parra, Andres; Cuerva, Juan M

2011-10-05

In a general sense, molecular electronics (ME) is the branch of nanotechnology which studies the application of molecular building blocks for the fabrication of electronic components. Among the different types of molecules, organic compounds have been revealed as promising candidates for ME, due to the easy access, great structural diversity and suitable electronic and mechanical properties. Thanks to these useful capabilities, organic molecules have been used to emulate electronic devices at the nanoscopic scale. In this feature article, we present the diverse strategies used to develop organic switches towards ME with special attention to non-volatile systems.

Electronic Structure Approach to Tunable Electronic Properties of Hybrid Organic-Inorganic Perovskites

NASA Astrophysics Data System (ADS)

Liu, Garnett; Huhn, William; Mitzi, David B.; Kanai, Yosuke; Blum, Volker

We present a study of the electronic structure of layered hybrid organic-inorganic perovskite (HOIP) materials using all-electron density-functional theory. Varying the nature of the organic and inorganic layers should enable systematically fine-tuning the carrier properties of each component. Using the HSE06 hybrid density functional including spin-orbit coupling (SOC), we validate the principle of tuning subsystem-specific parts of the electron band structures and densities of states in CH3NH3PbX3 (X=Cl, Br, I) compared to a modified organic component in layered (C6H5C2H4NH3) 2PbX4 (X=Cl, Br, I) and C20H22S4N2PbX4 (X=Cl, Br, I). We show that tunable shifts of electronic levels indeed arise by varying Cl, Br, I as the inorganic components, and CH3NH3+ , C6H5C2H4NH3+ , C20H22S4N22 + as the organic components. SOC is found to play an important role in splitting the conduction bands of the HOIP compounds investigated here. The frontier orbitals of the halide shift, increasing the gap, when Cl is substituted for Br and I.

Organic composition of aerosol particulate matter during a haze episode in Kuala Lumpur, Malaysia

NASA Astrophysics Data System (ADS)

Radzi Bin Abas, M.; Rahman, Noorsaadah A.; Omar, Nasr Yousef M. J.; Maah, M. Jamil; Abu Samah, Azizan; Oros, Daniel R.; Otto, Angelika; Simoneit, Bernd R. T.

The solvent-extractable compounds of urban airborne particulate matter were analyzed to determine the distributions of homologous and biomarker tracers. Samples were collected by high-volume air filtration during the haze episode of 1997 around the University of Malaya campus near Petaling Jaya, a suburb of Kuala Lumpur, Malaysia. These results show that the samples contain n-alkanes, n-alkan-2-ones, n-alkanols, methyl n-alkanoates, n-alkyl nitriles, n-alkanals, n-alkanoic acids, levoglucosan, PAHs, and UCM as the dominant components, with minor amounts of terpenoids, glyceryl esters and sterols, all derived from natural biogenic sources (vascular plant wax), from burning of biomass, and from anthropogenic utilization of fossil fuel products (lubricating oil, vehicle emissions, etc.). Some compositional differences are observed in the samples and greater atmospheric concentrations were found for almost all organic components in the samples collected near a roadway. The results interpreted in terms of major sources are due to local build-up of organic contaminants from vehicular emissions, smoke from biomass burning, and natural background as a result of the atmospheric stability during the haze episodes. The organic components transported in from areas outside the region, assuming all smoke components are external to the city, amount to about 30% of the total organic particle burden.

Chemical composition of gas-phase organic carbon emissions from motor vehicles and implications for ozone production.

PubMed

Gentner, Drew R; Worton, David R; Isaacman, Gabriel; Davis, Laura C; Dallmann, Timothy R; Wood, Ezra C; Herndon, Scott C; Goldstein, Allen H; Harley, Robert A

2013-10-15

Motor vehicles are major sources of gas-phase organic carbon, which includes volatile organic compounds (VOCs) and other compounds with lower vapor pressures. These emissions react in the atmosphere, leading to the formation of ozone and secondary organic aerosol (SOA). With more chemical detail than previous studies, we report emission factors for over 230 compounds from gasoline and diesel vehicles via two methods. First we use speciated measurements of exhaust emissions from on-road vehicles in summer 2010. Second, we use a fuel composition-based approach to quantify uncombusted fuel components in exhaust using the emission factor for total uncombusted fuel in exhaust together with detailed chemical characterization of liquid fuel samples. There is good agreement between the two methods except for products of incomplete combustion, which are not present in uncombusted fuels and comprise 32 ± 2% of gasoline exhaust and 26 ± 1% of diesel exhaust by mass. We calculate and compare ozone production potentials of diesel exhaust, gasoline exhaust, and nontailpipe gasoline emissions. Per mass emitted, the gas-phase organic compounds in gasoline exhaust have the largest potential impact on ozone production with over half of the ozone formation due to products of incomplete combustion (e.g., alkenes and oxygenated VOCs). When combined with data on gasoline and diesel fuel sales in the U.S., these results indicate that gasoline sources are responsible for 69-96% of emissions and 79-97% of the ozone formation potential from gas-phase organic carbon emitted by motor vehicles.

Diagnosis of aged prescribed burning plumes impacting an urban area.

PubMed

Lee, Sangil; Kim, Hyeon K; Yan, Bo; Cobb, Charles E; Hennigan, Chris; Nichols, Sara; Chamber, Michael; Edgerton, Eric S; Jansen, John J; Hu, Yongtao; Zheng, Mei; Weber, Rodney J; Russell, Armistead G

2008-03-01

An unanticipated wind shift led to the advection of plumes from two prescribed burning sites that impacted Atlanta, GA, producing a heavy smoke event late in the afternoon on February 28, 2007. Observed PM2.5 concentrations increased to over 140 microg/m3 and O3 concentrations up to 30 ppb in a couple of hours, despite the late hour in February when photochemistry is less vigorous. A detailed investigation of PM2.5 chemical composition and source apportionment analysis showed that the increase in PM2.5 mass was driven mainly by organic carbon (OC). However, both results from source apportionment and an observed nonlinear relationship between OC and PM2.5 potassium (K) indicate that the increased OC was not due solely to primary emissions. Most of the OC was water-soluble organic carbon (WSOC) and was dominated by hydrophobic compounds. The data are consistent with large enhancements in isoprenoid (isoprene and monoterpenes) and other volatile organic compounds emitted from prescribed burning that led to both significant O3 and secondary organic aerosol (SOA) production. Formation of oligomers from oxidation products of isoprenoid compounds or condensation of volatile organic compounds (VOCs) with multiple functional groups emitted during prescribed burning appears to be a major component of the secondary organic contributor of the SOA. The results from this study imply that enhanced emissions due to the fire itself and elevated temperature in the burning region should be considered in air quality models (e.g., receptor and emission-based models) to assess impacts of prescribed burning emissions on ambient air quality.

Analysis of switchgrass-derived bio-oil and associated aqueous phase generated in a semi-pilot scale auger pyrolyzer

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

Ren, Shoujie; Ye, X. Philip; Borole, Abhijeet P.

To efficiently utilize water-soluble compounds in bio-oil and evaluate the potential effects of these compounds on processes such as microbial electrolysis, our study investigated the physico-chemical properties of bio-oil and the associated aqueous phase generated from switchgrass using a semi-pilot scale auger pyrolyzer. Combining separation and detection strategies with organic solvent extraction, an array of analytical instruments and methods were used to identify and quantify the chemical constituents. Separation of an aqueous phase from crude bio-oil was achieved by adding water (water: crude bio-oil at 4:1 in weight), which resulted in a partition of 61 wt.% of the organic compoundsmore » into a bio-oil aqueous phase (BOAP). GC/MS analysis for BOAP identified over 40 compounds of which 16 were quantified. Acetic acid, propionic acid, and levoglucosan are the major components in BOAP. In addition, a significant portion of chemicals that have the potential to be upgraded to hydrocarbon fuels were extracted to BOAP (77 wt.% of the alcohols, 61 wt.% of the furans, and 52 wt.% of the phenolic compounds in crude bio-oil). Valorization of the BOAP may require conversion methods capable of accommodating a very broad substrate specificity. Ultimately, a better separation strategy is needed to selectively remove the acidic and polar components from crude bio-oil to improve economic feasibility of biorefinery operations.« less

Analysis of switchgrass-derived bio-oil and associated aqueous phase generated in a semi-pilot scale auger pyrolyzer

DOE PAGES

Ren, Shoujie; Ye, X. Philip; Borole, Abhijeet P.; ...

2016-03-30

To efficiently utilize water-soluble compounds in bio-oil and evaluate the potential effects of these compounds on processes such as microbial electrolysis, our study investigated the physico-chemical properties of bio-oil and the associated aqueous phase generated from switchgrass using a semi-pilot scale auger pyrolyzer. Combining separation and detection strategies with organic solvent extraction, an array of analytical instruments and methods were used to identify and quantify the chemical constituents. Separation of an aqueous phase from crude bio-oil was achieved by adding water (water: crude bio-oil at 4:1 in weight), which resulted in a partition of 61 wt.% of the organic compoundsmore » into a bio-oil aqueous phase (BOAP). GC/MS analysis for BOAP identified over 40 compounds of which 16 were quantified. Acetic acid, propionic acid, and levoglucosan are the major components in BOAP. In addition, a significant portion of chemicals that have the potential to be upgraded to hydrocarbon fuels were extracted to BOAP (77 wt.% of the alcohols, 61 wt.% of the furans, and 52 wt.% of the phenolic compounds in crude bio-oil). Valorization of the BOAP may require conversion methods capable of accommodating a very broad substrate specificity. Ultimately, a better separation strategy is needed to selectively remove the acidic and polar components from crude bio-oil to improve economic feasibility of biorefinery operations.« less

Diagnosing gastrointestinal illnesses using fecal headspace volatile organic compounds

PubMed Central

Chan, Daniel K; Leggett, Cadman L; Wang, Kenneth K

2016-01-01

Volatile organic compounds (VOCs) emitted from stool are the components of the smell of stool representing the end products of microbial activity and metabolism that can be used to diagnose disease. Despite the abundance of hydrogen, carbon dioxide, and methane that have already been identified in human flatus, the small portion of trace gases making up the VOCs emitted from stool include organic acids, alcohols, esters, heterocyclic compounds, aldehydes, ketones, and alkanes, among others. These are the gases that vary among individuals in sickness and in health, in dietary changes, and in gut microbial activity. Electronic nose devices are analytical and pattern recognition platforms that can utilize mass spectrometry or electrochemical sensors to detect these VOCs in gas samples. When paired with machine-learning and pattern recognition algorithms, this can identify patterns of VOCs, and thus patterns of smell, that can be used to identify disease states. In this review, we provide a clinical background of VOC identification, electronic nose development, and review gastroenterology applications toward diagnosing disease by the volatile headspace analysis of stool. PMID:26819529

Concentrations and distribution of manmade organic compounds in the Lake Tahoe Basin, Nevada and California, 1997-99

USGS Publications Warehouse

Lico, Michael S.; Pennington, Nyle

1999-01-01

The U.S. Geological Survey, in cooperation with the Tahoe Regional Planning Agency and the Lahontan Regional Water-Quality Control Board, sampled Lake Tahoe, major tributary streams to Lake Tahoe, and several other lakes in the Lake Tahoe Basin for manmade organic compounds during 1997-99. Gasoline components were found in all samples collected from Lake Tahoe during the summer boating season. Methyl tert-butyl ether (MTBE), benzene, toluene, ethylbenzene, and xylenes (BTEX) were the commonly detected compounds in these samples. Most samples from tributary streams and lakes with no motorized boating had no detectable concentrations of gasoline components. Motorized boating activity appears to be directly linked in space and time to the occurrence of these gasoline components. Other sources of gasoline components to Lake Tahoe, such as the atmosphere, surface runoff, and subsurface flow, are minor compared to the input by motorized boating. Water sampled from Lake Tahoe during mid-winter, when motorized boating activity is low, had no MTBE and only one sample had any detectable BTEX compounds. Soluble pesticides rarely were detected in water samples from the Lake Tahoe Basin. The only detectable concentrations of these compounds were in samples from Blackwood and Taylor Creeks collected during spring runoff. Concentrations found in these samples were low, in the 1 to 4 nanograms per liter range. Organochlorine compounds were detected in samples collected from semipermeable membrane devices (SPMD's) collected from Lake Tahoe, tributary streams, and Upper Angora Lake. In Lake Tahoe, SPMD samples collected offshore from urbanized areas contained the largest number and highest concentrations of organochlorine compounds. The most commonly detected organochlorine compounds were cis- and trans-chlordane, p, p'-DDE, and hexachlorobenzene. In tributary streams, SPMD samples collected during spring runoff generally had higher combined concentrations of organochlorine compounds than those collected during baseflow conditions. Upper Angora Lake had the fewest number of organochlorine compounds detected of all lake samples. Dioxins and furans were not detected in SPMD samples from two sites in Lake Tahoe or from two tributary streams. The number of polycyclic aromatic hydrocarbon (PAH) compounds and their combined concentrations generally were higher in samples from Lake Tahoe than those from tributary streams. Areas of high-motorized boating activity at Lake Tahoe had the largest number and highest concentrations of PAH's. PAH compounds were detected in samples from SPMD's in four of six tributary streams during spring runoff, all tributary streams during baseflow conditions, and at all lake sites. The most commonly detected PAH's in tributary streams during spring runoff were phenanthrene, fluoranthene, pyrene, and chrysene, and during baseflow conditions were phenanthrene, 1-methylphenanthrene, diethylnaphthalene, and pyrene. Upper Truckee River, which has an urban area in its drainage basin, had the largest number and highest combined concentration of PAH's of all stream samples. Bottom-sediment from Lake Tahoe had detectable concentrations of p-cresol, a phenol, in all but one sample. A sample collected near Chambers Lodge contained phenol at an estimated concentration of 4 micrograms per kilogram (?g/kg). Bottom-sediment samples from tributary streams had no detectable concentrations of organochlorine or PAH compounds. Several compounds were detected in bottom sediment from Upper Angora Lake at high concentrations. These compounds and their concentrations were p, p'-DDD (10 ?g/kg), p, p'-DDE (7.4 ?g/kg), 2,6-dimethylnaphthalene (estimated at 190 ?g/kg), pentachlorophenol (3,000 ?g/kg), and p-cresol (4,400 ?g/kg).

Supercritical fluid extraction of the non-polar organic compounds in meteorites

NASA Astrophysics Data System (ADS)

Sephton, M. A.; Pillinger, C. T.; Gilmour, I.

2001-01-01

The carbonaceous chondrite meteorites contain a variety of extraterrestrial organic molecules. These organic components provide a valuable insight into the formation and evolution of the solar system. Attempts at obtaining and interpreting this information source are hampered by the small sample sizes available for study and the interferences from terrestrial contamination. Supercritical fluid extraction represents an efficient and contamination-free means of isolating extraterrestrial molecules. Gas chromatography-mass spectrometry analyses of extracts from Orgueil and Cold Bokkeveld reveal a complex mixture of free non-polar organic molecules which include normal alkanes, isoprenoid alkanes, tetrahydronaphthalenes and aromatic hydrocarbons. These organic assemblages imply contributions from both terrestrial and extraterrestrial sources.

Polymer coated quartz crystal microbalance sensors for detection of volatile organic compounds in gas mixtures.

PubMed

Si, Pengchao; Mortensen, John; Komolov, Alexei; Denborg, Jens; Møller, Preben Juul

2007-08-06

By coating different conducting polymers of thiophene and its derivatives on quartz crystal microbalance (QCM) sensor surfaces, new novel QCM gas sensors have been produced in two simple ways, which could classify testing gas samples of volatile organic compounds (VOCs) gases. Principle components analysis (PCA) has been performed based on the QCM measurement results, which shows that our QCM sensors array has very good utilizing potential on sensing both polar and low-polar/nonpolar VOC gases. The sensitivity, selectivity, reproducibility and detection limit of QCM sensors have also been discussed. Quantitative variation of sensitivity response with the increasing concentration has been studied. (PLS) analysis and prediction of concentrations of single gas in mixtures have been carried out.

Sulfonates: A novel class of organic sulfur compounds in marine sediments

NASA Astrophysics Data System (ADS)

Vairavamurthy, Appathurai; Zhou, Weiqing; Eglinton, Timothy; Manowitz, Bernard

1994-11-01

X-ray absorption near-edge structure spectroscopy (XANES) used to measure sulfur speciation in a variety of organic-rich marine sediments has established sulfonates as a novel and major component of sedimentary organic sulfur. The origins of sulfonates in sediments are not clear, although both biological and geochemical mechanisms are possible. The accumulation of oxidized sulfonate sulfur in reducing marine sediments was not known previously; hence, a new perspective in sulfur geochemistry is established. The biogeochemical implications of the presence of sulfonates in marine sediments are discussed.

State of research: environmental pathways and food chain transfer.

PubMed Central

Vaughan, B E

1984-01-01

Data on the chemistry of biologically active components of petroleum, synthetic fuel oils, certain metal elements and pesticides provide valuable generic information needed for predicting the long-term fate of buried waste constituents and their likelihood of entering food chains. Components of such complex mixtures partition between solid and solution phases, influencing their mobility, volatility and susceptibility to microbial transformation. Estimating health hazards from indirect exposures to organic chemicals involves an ecosystem's approach to understanding the unique behavior of complex mixtures. Metabolism by microbial organisms fundamentally alters these complex mixtures as they move through food chains. Pathway modeling of organic chemicals must consider the nature and magnitude of food chain transfers to predict biological risk where metabolites may become more toxic than the parent compound. To obtain predictions, major areas are identified where data acquisition is essential to extend our radiological modeling experience to the field of organic chemical contamination. PMID:6428875

Hygroscopicity of organic surrogate compounds from biomass burning and their effect on the efflorescence of ammonium sulfate in mixed aerosol particles

NASA Astrophysics Data System (ADS)

Lei, Ting; Zuend, Andreas; Cheng, Yafang; Su, Hang; Wang, Weigang; Ge, Maofa

2018-01-01

Hygroscopic growth factors of organic surrogate compounds representing biomass burning and mixed organic-inorganic aerosol particles exhibit variability during dehydration experiments depending on their chemical composition, which we observed using a hygroscopicity tandem differential mobility analyzer (HTDMA). We observed that levoglucosan and humic acid aerosol particles release water upon dehumidification in the range from 90 to 5 % relative humidity (RH). However, 4-Hydroxybenzoic acid aerosol particles remain in the solid state upon dehumidification and exhibit a small shrinking in size at higher RH compared to the dry size. For example, the measured growth factor of 4-hyroxybenzoic acid aerosol particles is ˜ 0.96 at 90 % RH. The measurements were accompanied by RH-dependent thermodynamic equilibrium calculations using the Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients (AIOMFAC) model and Extended Aerosol Inorganics Model (E-AIM), the Zdanovskii-Stokes-Robinson (ZSR) relation, and a fitted hygroscopicity expression. We observed several effects of organic components on the hygroscopicity behavior of mixtures containing ammonium sulfate (AS) in relation to the different mass fractions of organic compounds: (1) a shift of efflorescence relative humidity (ERH) of ammonium sulfate to higher RH due to the presence of 25 wt % levoglucosan in the mixture. (2) There is a distinct efflorescence transition at 25 % RH for mixtures consisting of 25 wt % of 4-hydroxybenzoic acid compared to the ERH at 35 % for organic-free AS particles. (3) There is indication for a liquid-to-solid phase transition of 4-hydroxybenzoic acid in the mixed particles during dehydration. (4) A humic acid component shows no significant effect on the efflorescence of AS in mixed aerosol particles. In addition, consideration of a composition-dependent degree of dissolution of crystallization AS (solid-liquid equilibrium) in the AIOMFAC and E-AIM models leads to a relatively good agreement between models and observed growth factors, as well as ERH of AS in the mixed system. The use of the ZSR relation leads to good agreement with measured diameter growth factors of aerosol particles containing humic acid and ammonium sulfate. Lastly, two distinct mixtures of organic surrogate compounds, including levoglucosan, 4-hydroxybenzoic acid, and humic acid, were used to represent the average water-soluble organic carbon (WSOC) fractions observed during the wet and dry seasons in the central Amazon Basin. A comparison of the organic fraction's hygroscopicity parameter for the simple mixtures, e.g., κ ≈ 0.12 to 0.15 for the wet-season mixture in the 90 to 40 % RH range, shows good agreement with field data for the wet season in the Amazon Basin (WSOC κ ≈ 0.14±0.06 at 90 % RH). This suggests that laboratory-generated mixtures containing organic surrogate compounds and ammonium sulfate can be used to mimic, in a simplified manner, the chemical composition of ambient aerosols from the Amazon Basin for the purpose of RH-dependent hygroscopicity studies.

TyPol - a new methodology for organic compounds clustering based on their molecular characteristics and environmental behavior.

PubMed

Servien, Rémi; Mamy, Laure; Li, Ziang; Rossard, Virginie; Latrille, Eric; Bessac, Fabienne; Patureau, Dominique; Benoit, Pierre

2014-09-01

Following legislation, the assessment of the environmental risks of 30000-100000 chemical substances is required for their registration dossiers. However, their behavior in the environment and their transfer to environmental components such as water or atmosphere are studied for only a very small proportion of the chemical in laboratory tests or monitoring studies because it is time-consuming and/or cost prohibitive. Therefore, the objective of this work was to develop a new methodology, TyPol, to classify organic compounds, and their degradation products, according to both their behavior in the environment and their molecular properties. The strategy relies on partial least squares analysis and hierarchical clustering. The calculation of molecular descriptors is based on an in silico approach, and the environmental endpoints (i.e. environmental parameters) are extracted from several available databases and literature. The classification of 215 organic compounds inputted in TyPol for this proof-of-concept study showed that the combination of some specific molecular descriptors could be related to a particular behavior in the environment. TyPol also provided an analysis of similarities (or dissimilarities) between organic compounds and their degradation products. Among the 24 degradation products that were inputted, 58% were found in the same cluster as their parents. The robustness of the method was tested and shown to be good. TyPol could help to predict the environmental behavior of a "new" compound (parent compound or degradation product) from its affiliation to one cluster, but also to select representative substances from a large data set in order to answer some specific questions regarding their behavior in the environment. Copyright © 2014 Elsevier Ltd. All rights reserved.

A regional study of the seasonal variation in the molecular composition of rainwater

NASA Astrophysics Data System (ADS)

Cottrell, Barbara A.; Gonsior, Michael; Isabelle, Lorne M.; Luo, W.; Perraud, Véronique; McIntire, Theresa M.; Pankow, James F.; Schmitt-Kopplin, Philippe; Cooper, William J.; Simpson, André J.

2013-10-01

Rainwater is not only a critical source of drinking and agricultural water but it plays a key role in the fate and transport of contaminants through their removal by wet deposition. Rainwater is a complex mixture of organic compounds yet despite its importance its spatial and temporal variability are not well understood and less than 50% of the organic matter has been characterized. In-depth analytical approaches were used in this study to characterize the seasonal variation in rainwater composition. Rainwater samples were collected over a one-year period in Scarborough, Ontario, Canada. The seasonal variation of atmospheric organic carbon (AOC) in rainwater was analyzed by excitation-emission matrix spectroscopy (EEMs), 1D and 2D NMR with compound identification by spectral database matching, GC-MS, FT-ICR-MS, and GC × GC-TOFMS. This combination of techniques provided four complementary datasets, with less than 10% overlap, of anthropogenic and biogenic AOC. NMR with database matching identified over 100 compounds, primarily carboxylic acids, carbohydrates, and nitrogen-containing compounds. GC × GC-TOFMS analysis identified 344 compounds in two rain events with 33% of the compounds common to both events. FT-ICR-MS generated a seasonally dependent profile of 1226-1575 molecular ions of CHO, CHOS, and CHON elemental composition. FT-ICR-MS and GC × GC-TOFMS datasets were compared using van Krevelen diagrams (H/C vs. O/C), the H/C ratio vs. mass/charge (m/z), and the carbon oxidation state/carbon number matrix. Fluorescence patterns were correlated with NMR results resulting in the identification one seasonally-dependent component of chromophoric dissolved organic matter (CDOM). This study demonstrated the importance of using of an integrated analytical approach to monitor the compositional variation of AOC.

New molecular insights into the pools and mechanisms of Arctic soil organic matter decomposition under warming

NASA Astrophysics Data System (ADS)

Gu, B.

2017-12-01

It is estimated that Arctic permafrost soils store approximately half of the global belowground organic carbon, which is susceptible to microbial decomposition under warming climate. Studies have shown that rates of soil organic carbon (SOC) decomposition are controlled not only by temperature but also SOC substrate quality or chemical composition. However, detailed molecular-scale characterization of SOC and its susceptibility to degradation are lacking, due to extremely complex nature of SOC. Here, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) was utilized to determine compositional changes of SOC during a microcosm warming experiment using tundra soils that were collected from the Barrow Environmental Observatory in Alaska, USA. Soil microcosm incubation was conducted with both organic and mineral active layer soils at two temperatures (-2°C and 8°C) up to 122 days, and water-extractable SOC was analyzed. Results indicate that peptides, amino sugars, and carbohydrate-like compounds are among the most labile SOC compounds to be degraded, with nitrogen-containing compounds degrading at a much faster rate than those containing no nitrogen. Refractory SOC components are dominated by the lignin- or tannin-like compounds and, to a less extent, the aliphatic compounds. Additionally, elemental ratios of O:C, H:C, and N:C were found to decrease with incubation time, and SOC in the mineral soil exhibited lower O:C and N:C ratios than those of the organic-rich soil. A biodegradation index is proposed to facilitate the incorporation of mass spectrometry data into mechanistic models of SOC degradation and thus improved prediction model of climate feedbacks in the Arctic.

New molecular insights into the pools and mechanisms of Arctic soil organic matter decomposition under warming

NASA Astrophysics Data System (ADS)

Gilbert, A.; Yamada, K.; Julien, M.; Yoshida, N.; Remaud, G.; Robins, R.

2016-12-01

It is estimated that Arctic permafrost soils store approximately half of the global belowground organic carbon, which is susceptible to microbial decomposition under warming climate. Studies have shown that rates of soil organic carbon (SOC) decomposition are controlled not only by temperature but also SOC substrate quality or chemical composition. However, detailed molecular-scale characterization of SOC and its susceptibility to degradation are lacking, due to extremely complex nature of SOC. Here, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) was utilized to determine compositional changes of SOC during a microcosm warming experiment using tundra soils that were collected from the Barrow Environmental Observatory in Alaska, USA. Soil microcosm incubation was conducted with both organic and mineral active layer soils at two temperatures (-2°C and 8°C) up to 122 days, and water-extractable SOC was analyzed. Results indicate that peptides, amino sugars, and carbohydrate-like compounds are among the most labile SOC compounds to be degraded, with nitrogen-containing compounds degrading at a much faster rate than those containing no nitrogen. Refractory SOC components are dominated by the lignin- or tannin-like compounds and, to a less extent, the aliphatic compounds. Additionally, elemental ratios of O:C, H:C, and N:C were found to decrease with incubation time, and SOC in the mineral soil exhibited lower O:C and N:C ratios than those of the organic-rich soil. A biodegradation index is proposed to facilitate the incorporation of mass spectrometry data into mechanistic models of SOC degradation and thus improved prediction model of climate feedbacks in the Arctic.

Volatile Compounds from the Different Organs of Houttuynia cordata and Litsea cubeba (L. citriodora).

PubMed

Asakawa, Yoshinori; Tomiyama, Kenichi; Sakurai, Kazutoshi; Kawakami, Yukihiro; Yaguchi, Yoshihiro

2017-08-01

The volatile compounds obtained from the different organs of Houttuynia cordata (Saururaceae) and Litsea cubeba (Lauraceae) were analyzed by Gas Chromatography/Mass Spectrometry (GC/MS), Headspace Solid Phase Micro Extraction-Gas Chromatography/Mass Spectrometry (HS-SPME-GC/MS), and GC/olfactometry (GC/O). The major component of all parts of H. cordata is assigned as 4-tridecanone. Each organ produces myrcene as the major monoterpenoid. The major monoterpene in the rhizomes and roots was β-pinene instead of myrcene. 1-Decanal which was responsible for the unpleasant odor of this plant, was the predominant polyketide in both leaves and stems. The presence of 1-decanal was very poor in flowers, stem collected in summer, rhizomes, and roots. GC/MS analyses were very simple in case of the crude extracts of flowers. The content of sesquiterpenoids was extremely poor. (8Z)-Heptadecene, geranial, and neral were detected as the major components in Litsea cubeba. Odor-contributing components by GC/O analysis of the ether extract of the fresh flowers of L. cubeba were neral and geranial which played an important role in sweet-lemon fragrance of the flowers. The role of a high content of (8Z)-heptadecene was still unknown but it might play a significant role in the dispersion of the volatile monoterpene hydrocarbons and aldehydes. The flower volatiles of the Japanese L. cubeba were chemically quite different from those of the Chinese same species.

Real-time detection of organic contamination events in water distribution systems by principal components analysis of ultraviolet spectral data.

PubMed

Zhang, Jian; Hou, Dibo; Wang, Ke; Huang, Pingjie; Zhang, Guangxin; Loáiciga, Hugo

2017-05-01

The detection of organic contaminants in water distribution systems is essential to protect public health from potential harmful compounds resulting from accidental spills or intentional releases. Existing methods for detecting organic contaminants are based on quantitative analyses such as chemical testing and gas/liquid chromatography, which are time- and reagent-consuming and involve costly maintenance. This study proposes a novel procedure based on discrete wavelet transform and principal component analysis for detecting organic contamination events from ultraviolet spectral data. Firstly, the spectrum of each observation is transformed using discrete wavelet with a coiflet mother wavelet to capture the abrupt change along the wavelength. Principal component analysis is then employed to approximate the spectra based on capture and fusion features. The significant value of Hotelling's T 2 statistics is calculated and used to detect outliers. An alarm of contamination event is triggered by sequential Bayesian analysis when the outliers appear continuously in several observations. The effectiveness of the proposed procedure is tested on-line using a pilot-scale setup and experimental data.

Survey and analysis of crystal polymorphism in organic structures

PubMed Central

Kaur, Ramanpreet

2018-01-01

With the intention of producing the most comprehensive treatment of the prevalence of crystal polymorphism among structurally characterized materials, all polymorphic compounds flagged as such within the Cambridge Structural Database (CSD) are analysed and a list of crystallographically characterized organic polymorphic compounds is assembled. Classifying these structures into subclasses of anhydrates, salts, hydrates, non-hydrated solvates and cocrystals reveals that there are significant variations in polymorphism prevalence as a function of crystal type, a fact which has not previously been recognized in the literature. It is also shown that, as a percentage, polymorphic entries are decreasing temporally within the CSD, with the notable exception of cocrystals, which continue to rise at a rate that is a constant fraction of the overall entries. Some phenomena identified that require additional scrutiny include the relative prevalence of temperature-induced phase transitions among organic salts and the paucity of polymorphism in crystals with three or more chemical components. PMID:29765601

Comparative Study of the Volatile Components of Fresh and Fermented Flowers of Alnus sieboldiana (Betulaceae).

PubMed

Ab Ghani, Nurunajah; Ismail, Nor Hadiani; Asakawa, Yoshinori

2016-02-01

Analysis of the volatile components present in the fresh male and female flowers and young leaves shows that 2-phenylethanol is the major component in all these three organs, which play a significant role in the strong resinous aromatic odor. The male flowers contained styrene as a second major compound. The level of styrene does not affect the male flowers odor concentration. The level of β-phenylethyl cinnamate and trans-methyl cinnamate in the fermented male flowers decreased as the fermentation time increased. This was due to the Penicillium enzymatic action on the fermented male flowers.

Changes in the dissolved organic matter leaching from soil under severe temperature and N-deposition.

PubMed

Nguyen, Hang Vo-Minh; Choi, Jung Hyun

2015-06-01

In this study, we conducted growth chamber experiments using three types of soil (wetland, rice paddy, and forest) under the conditions of a severe increase in the temperature and N-deposition in order to investigate how extreme weather influences the characteristics of the dissolved organic matter (DOM) leaching from different soil types. This leachate controls the quantity and quality of DOM in surface water systems. After 5 months of incubation, the dissolved organic carbon (DOC) concentrations decreased in the range of 21.1 to 88.9 %, while the specific UV absorption (SUVA) values increased substantially in the range of 19.9 to 319.9 % for all of the samples. Higher increases in the SUVA values were observed at higher temperatures, whereas the opposite trend was observed for samples with N-addition. The parallel factor analysis (PARAFAC) results showed that four fluorescence components: terrestrial humic-like (component 1 (C1)), microbial humic-like (component 2 (C2)), protein-like (component 3 (C3)), and anthropogenic humic-like (component 4 (C4)) constituted the fluorescence matrices of soil samples. During the experiment, labile DOM from the soils was consumed and transformed into resistant aromatic carbon structures and less biodegradable components via microbial processes. The principle component analysis (PCA) results indicated that severe temperatures and N-deposition could enhance the contribution of the aromatic carbon compounds and humic-like components in the soil samples.

Chemical composition of atmospheric aerosols resolved via positive matrix factorization

NASA Astrophysics Data System (ADS)

Äijälä, Mikko; Junninen, Heikki; Heikkinen, Liine; Petäjä, Tuukka; Kulmala, Markku; Worsnop, Douglas; Ehn, Mikael

2017-04-01

Atmospheric particulate matter is a complex mixture of various chemical species such as organic compounds, sulfates, nitrates, ammonia, chlorides, black carbon and sea salt. As aerosol chemical composition strongly influences aerosol climate effects (via cloud condensation nucleus activation, hygroscopic properties, aerosol optics, volatility and condensation) as well as health effects (toxicity, carcinogenicity, particle morphology), detailed understanding of atmospheric fine particle composition is widely beneficial for understanding these interactions. Unfortunately the comprehensive, detailed measurement of aerosol chemistry remains difficult due to the wide range of compounds present in the atmosphere as well as for the miniscule mass of the particles themselves compared to their carrier gas. Aerosol mass spectrometer (AMS; Canagaratna et al., 2007) is an instrument often used for characterization of non-refractive aerosol types: the near-universal vaporization and ionisation technique allows for measurement of most atmospheric-relevant compounds (with the notable exception of refractory matter such as sea salt, black carbon, metals and crustal matter). The downside of the hard ionisation applied is extensive fragmentation of sample molecules. However, the apparent loss of information in fragmentation can be partly offset by applying advanced statistical methods to extract information from the fragmentation patterns. In aerosol mass spectrometry statistical analysis methods, such as positive matrix factorization (PMF; Paatero, 1999) are usually applied for aerosol organic component only, to keep the number of factors to be resolved manageable, to retain the inorganic components for solution validation via correlation analysis, and to avoid inorganic species dominating the factor model. However, this practice smears out the interactions between organic and inorganic chemical components, and hinders the understanding of the connections between primary and secondary aerosols via atmospheric physicochemical processes (e.g. condensation and evaporation of gases) and on the other hand the potential non-linear summation (Spracklen et al., 2011 2011) of anthropogenic and biogenic aerosol emissions. From the perspective of statistical analysis there is no definite reason why inorganics could not be included, as long as their uncertainties are estimated correctly and their influence is properly weighted in the factor model. For result validation, external, additional information available from most measurement sites, such as correlations with trace gas concentrations or size distribution derived, mode-specific mass loadings can be used instead of AMS inorganics. In recent analyses, nitrate compounds have already been added to PMF analyses and shown to interact with organic semi-volatile compounds (Hao et al., 2014). In this study we tested including all the default AMS chemical species, i.e. organics, sulfates, nitrates, ammonia and chlorides, in a PMF analysis, and present potential interpretations of the results with regard to aerosol sources and the chemical processes shaping the aerosol types. In addition to resolving organic-dominated aerosol classes, the results shed light on inorganic salt formation and may imply formation of organics salts. Canagaratna, M. et al. (2007). Mass Spectrom Rev., 26:185-222. Hao, L. et al. (2014). Atmos. Chem. Phys., 14, 13483-13495. Paatero, P. (1999). J Comput Graph Stat, 8: 854-888. Spracklen, D. et al (2011) Atmos. Chem. Phys., 11, 12109-12136.

Emissions of organic compounds from produced water ponds II: Evaluation of flux chamber measurements with inverse-modeling techniques.

PubMed

Tran, Huy N Q; Lyman, Seth N; Mansfield, Marc L; O'Neil, Trevor; Bowers, Richard L; Smith, Ann P; Keslar, Cara

2018-07-01

In this study, the authors apply two different dispersion models to evaluate flux chamber measurements of emissions of 58 organic compounds, including C2-C11 hydrocarbons and methanol, ethanol, and isopropanol from oil- and gas-produced water ponds in the Uintah Basin. Field measurement campaigns using the flux chamber technique were performed at a limited number of produced water ponds in the basin throughout 2013-2016. Inverse-modeling results showed significantly higher emissions than were measured by the flux chamber. Discrepancies between the two methods vary across hydrocarbon compounds and are largest in alcohols due to their physical chemistries. This finding, in combination with findings in a related study using the WATER9 wastewater emission model, suggests that the flux chamber technique may underestimate organic compound emissions, especially alcohols, due to its limited coverage of the pond area and alteration of environmental conditions, especially wind speed. Comparisons of inverse-model estimations with flux chamber measurements varied significantly with the complexity of pond facilities and geometries. Both model results and flux chamber measurements suggest significant contributions from produced water ponds to total organic compound emission from oil and gas productions in the basin. This research is a component of an extensive study that showed significant amount of hydrocarbon emissions from produced water ponds in the Uintah Basin, Utah. Such findings have important meanings to air quality management agencies in developing control strategies for air pollution in oil and gas fields, especially for the Uintah Basin in which ozone pollutions frequently occurred in winter seasons.

Uniaxially oriented polycrystalline thin films and air-stable n-type transistors based on donor-acceptor semiconductor (diC8BTBT)(FnTCNQ) [n = 0, 2, 4

NASA Astrophysics Data System (ADS)

Shibata, Yosei; Tsutsumi, Jun'ya; Matsuoka, Satoshi; Matsubara, Koji; Yoshida, Yuji; Chikamatsu, Masayuki; Hasegawa, Tatsuo

2015-04-01

We report the fabrication of high quality thin films for semiconducting organic donor-acceptor charge-transfer (CT) compounds, (diC8BTBT)(FnTCNQ) (diC8BTBT = 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene and FnTCNQ [n = 0,2,4] = fluorinated derivatives of 7,7,8,8,-tetracyanoquinodimethane), which have a high degree of layered crystallinity. Single-phase and uniaxially oriented polycrystalline thin films of the compounds were obtained by co-evaporation of the component donor and acceptor molecules. Organic thin-film transistors (OTFTs) fabricated with the compound films exhibited n-type field-effect characteristics, showing a mobility of 6.9 × 10-2 cm2/V s, an on/off ratio of 106, a sub-threshold swing of 0.8 V/dec, and an excellent stability in air. We discuss the suitability of strong intermolecular donor-acceptor interaction and the narrow CT gap nature in compounds for stable n-type OTFT operation.

Anaerobic biodegradability and methanogenic toxicity of key constituents in copper chemical mechanical planarization effluents of the semiconductor industry.

PubMed

Hollingsworth, Jeremy; Sierra-Alvarez, Reyes; Zhou, Michael; Ogden, Kimberly L; Field, Jim A

2005-06-01

Copper chemical mechanical planarization (CMP) effluents can account for 30-40% of the water discharge in semiconductor manufacturing. CMP effluents contain high concentrations of soluble copper and a complex mixture of organic constituents. The aim of this study is to perform a preliminary assessment of the treatability of CMP effluents in anaerobic sulfidogenic bioreactors inoculated with anaerobic granular sludge by testing individual compounds expected in the CMP effluents. Of all the compounds tested (copper (II), benzotriazoles, polyethylene glycol (M(n) 300), polyethylene glycol (M(n) 860) monooleate, perfluoro-1-octane sulfonate, citric acid, oxalic acid and isopropanol) only copper was found to be inhibitory to methanogenic activity at the concentrations tested. Most of the organic compounds tested were biodegradable with the exception of perfluoro-1-octane sulfonate and benzotriazoles under sulfate reducing conditions and with the exception of the same compounds as well as Triton X-100 under methanogenic conditions. The susceptibility of key components in CMP effluents to anaerobic biodegradation combined with their low microbial inhibition suggest that CMP effluents should be amenable to biological treatment in sulfate reducing bioreactors.

Gas-particle partitioning of atmospheric aerosols: interplay of physical state, non-ideal mixing and morphology.

PubMed

Shiraiwa, Manabu; Zuend, Andreas; Bertram, Allan K; Seinfeld, John H

2013-07-21

Atmospheric aerosols, comprising organic compounds and inorganic salts, play a key role in air quality and climate. Mounting evidence exists that these particles frequently exhibit phase separation into predominantly organic and aqueous electrolyte-rich phases. As well, the presence of amorphous semi-solid or glassy particle phases has been established. Using the canonical system of ammonium sulfate mixed with organics from the ozone oxidation of α-pinene, we illustrate theoretically the interplay of physical state, non-ideality, and particle morphology affecting aerosol mass concentration and the characteristic timescale of gas-particle mass transfer. Phase separation can significantly affect overall particle mass and chemical composition. Semi-solid or glassy phases can kinetically inhibit the partitioning of semivolatile components and hygroscopic growth, in contrast to the traditional assumption that organic compounds exist in quasi-instantaneous gas-particle equilibrium. These effects have significant implications for the interpretation of laboratory data and the development of improved atmospheric air quality and climate models.

Self-assembly micro optical filter

NASA Astrophysics Data System (ADS)

Zhang, Ping (Cerina); Le, Kevin; Malalur-Nagaraja-Rao, Smitha; Hsu, Lun-Chen; Chiao, J.-C.

2006-01-01

Optical communication and sensor industry face critical challenges in manufacturing for system integration. Due to the assembly complexity and integration platform variety, micro optical components require costly alignment and assembly procedures, in which many required manual efforts. Consequently, self-assembly device architectures have become a great interest and could provide major advantages over the conventional optical devices. In this paper, we discussed a self-assembly integration platform for micro optical components. To demonstrate the adaptability and flexibility of the proposed optical device architectures, we chose a commercially available MEMS fabrication foundry service - MUMPs (Multi-User MEMS Process). In this work, polysilicon layers of MUMPS are used as the 3-D structural material for construction of micro component framework and actuators. However, because the polysilicon has high absorption in the visible and near infrared wavelength ranges, it is not suitable for optical interaction. To demonstrate the required optical performance, hybrid integration of materials was proposed and implemented. Organic compound materials were applied on the silicon-based framework to form the required optical interfaces. Organic compounds provide good optical transparency, flexibility to form filters or lens and inexpensive manufacturing procedures. In this paper, we have demonstrated a micro optical filter integrated with self-assembly structures. We will discuss the self-assembly mechanism, optical filter designs, fabrication issues and results.

Improving and assessing vapour pressure estimation methods for organic compounds of atmospheric relevance using a Knudsen Effusion Mass Spectrometer (KEMS)

NASA Astrophysics Data System (ADS)

Booth, A. M.; Topping, D. O.; McFiggans, G. B.; Garforth, A.; Percival, C. J.

2009-12-01

Aerosol particles influence climate directly through the scattering and absorbing radiation and indirectly through their role as cloud condensation nuclei (CCN). Traditionally, models aiming to capture the behaviour of aerosols in the atmosphere have concentrated on the role of inorganic compounds. However, organic components, covering a huge range of chemical and physical properties (Jacobson et.al., 2000), may constitute a significant fraction depending on location (Houghton et.al., 2001). Knowledge of pure component vapour pressures is essential for calculations of gas/particle partitioning. There are many methods of estimating vapour pressures but most of the experimental data collected to date has been for intermediate or high pressure compounds (and often measured at temperatures considerably above ambient) and the proportion of experimental data for low (less than 100Pa) vapour pressure compounds has been very small. Hence the datasets used for developing the estimation methods have reflected this bias in addition to the fact that components studied tend to have one or two functional groups at the most. Thus it is unsurprising that some of the estimation methods can give errors in vapour pressure of several orders of magnitude for multifunctional compounds at ambient temperatures. Knudsen Effusion Mass Spectrometer (KEMS) has been used to measure solid state vapour pressures for multifunctional organic compounds based on dicarboxylic acids (Booth et al 2009). In the atmosphere these compounds are likely to exist in the sub-cooled state so Differential Scanning Calorimetry (DSC) was used to obtain thermochemical data to effect a correction between solid and sub-cooled vapour pressures. The group contribution method of Nanoolal and co-workers (Nanoolal et al., 2008) is one of the best predictive methods in terms of reproducing available low volatility vapour pressure data (barley et al., 2009). The Nanoolal method relies on the use of primary and secondary functional groups and interaction parameters, derived from experimental data, to reliably predict boiling points and vapour pressures. A sensitivity study was undertaken to establish the impact of the new experimentally determined vapour pressures on partitioning models. Jacobson, M.C., et al. Rev Geophys, 38 (2), 267-294, 2000. Houghton et al. Climate Change 2001: The Scientific Basis. Contribution of Working Group 1 to the Third Assessment Report of the IPCC., 881 pp., Cambridge University Press, 2001. Johnson, D. , et al. Atmo. Chem. Phys., Vol. 6, 419-431, 2006 Yu, J. Z., et al. J Atmos Chem. 34, 207-258, 1999 Booth, A.M. et al Atmos. Meas. Tech.,2,355-361, 2009 Nanoolal, Y. et al Fluid Phase Equilibria, 269,117-133., 2008. Barley, M. et al Atmos. Chem. Phys., -,to be submitted.

Compounds from silicones alter enzyme activity in curing barnacle glue and model enzymes.

PubMed

Rittschof, Daniel; Orihuela, Beatriz; Harder, Tilmann; Stafslien, Shane; Chisholm, Bret; Dickinson, Gary H

2011-02-17

Attachment strength of fouling organisms on silicone coatings is low. We hypothesized that low attachment strength on silicones is, in part, due to the interaction of surface available components with natural glues. Components could alter curing of glues through bulk changes or specifically through altered enzyme activity. GC-MS analysis of silicone coatings showed surface-available siloxanes when the coatings were gently rubbed with a cotton swab for 15 seconds or given a 30 second rinse with methanol. Mixtures of compounds were found on 2 commercial and 8 model silicone coatings. The hypothesis that silicone components alter glue curing enzymes was tested with curing barnacle glue and with commercial enzymes. In our model, barnacle glue curing involves trypsin-like serine protease(s), which activate enzymes and structural proteins, and a transglutaminase which cross-links glue proteins. Transglutaminase activity was significantly altered upon exposure of curing glue from individual barnacles to silicone eluates. Activity of purified trypsin and, to a greater extent, transglutaminase was significantly altered by relevant concentrations of silicone polymer constituents. Surface-associated silicone compounds can disrupt glue curing and alter enzyme properties. Altered curing of natural glues has potential in fouling management.

Compounds from Silicones Alter Enzyme Activity in Curing Barnacle Glue and Model Enzymes

PubMed Central

Rittschof, Daniel; Orihuela, Beatriz; Harder, Tilmann; Stafslien, Shane; Chisholm, Bret; Dickinson, Gary H.

2011-01-01

Background Attachment strength of fouling organisms on silicone coatings is low. We hypothesized that low attachment strength on silicones is, in part, due to the interaction of surface available components with natural glues. Components could alter curing of glues through bulk changes or specifically through altered enzyme activity. Methodology/Principal Findings GC-MS analysis of silicone coatings showed surface-available siloxanes when the coatings were gently rubbed with a cotton swab for 15 seconds or given a 30 second rinse with methanol. Mixtures of compounds were found on 2 commercial and 8 model silicone coatings. The hypothesis that silicone components alter glue curing enzymes was tested with curing barnacle glue and with commercial enzymes. In our model, barnacle glue curing involves trypsin-like serine protease(s), which activate enzymes and structural proteins, and a transglutaminase which cross-links glue proteins. Transglutaminase activity was significantly altered upon exposure of curing glue from individual barnacles to silicone eluates. Activity of purified trypsin and, to a greater extent, transglutaminase was significantly altered by relevant concentrations of silicone polymer constituents. Conclusions/Significance Surface-associated silicone compounds can disrupt glue curing and alter enzyme properties. Altered curing of natural glues has potential in fouling management. PMID:21379573

Vegetable Oils as Alternative Solvents for Green Oleo-Extraction, Purification and Formulation of Food and Natural Products.

PubMed

Yara-Varón, Edinson; Li, Ying; Balcells, Mercè; Canela-Garayoa, Ramon; Fabiano-Tixier, Anne-Sylvie; Chemat, Farid

2017-09-05

Since solvents of petroleum origin are now strictly regulated worldwide, there is a growing demand for using greener, bio-based and renewable solvents for extraction, purification and formulation of natural and food products. The ideal alternative solvents are non-volatile organic compounds (VOCs) that have high dissolving power and flash point, together with low toxicity and less environmental impact. They should be obtained from renewable resources at a reasonable price and be easy to recycle. Based on the principles of Green Chemistry and Green Engineering, vegetable oils could become an ideal alternative solvent to extract compounds for purification, enrichment, or even pollution remediation. This review presents an overview of vegetable oils as solvents enriched with various bioactive compounds from natural resources, as well as the relationship between dissolving power of non-polar and polar bioactive components with the function of fatty acids and/or lipid classes in vegetable oils, and other minor components. A focus on simulation of solvent-solute interactions and a discussion of polar paradox theory propose a mechanism explaining the phenomena of dissolving polar and non-polar bioactive components in vegetable oils as green solvents with variable polarity.

Thermal Desorption/GCMS Analysis of Astrobiologically Relevant Organic Materials

NASA Technical Reports Server (NTRS)

McDonald, Gene D.

2001-01-01

Several macromolecular organic materials, both biologically-derived (type II kerogen and humic acid) and abiotic in origin (Murchison insoluble organic material, cyanide polymer, and Titan tholin) were subjected to thermal desorption using a Chromatoprobe attachment on a Varian Saturn 2000 GCMS system. Each sample was heated sequentially at 100, 200, and 300 C to release volatile components. The evolved compounds were then separated on a Supelco EC-1 dimethylsilica GC column and detected by the Saturn 2000 ion trap mass spectrometer. The various types of macromolecular organic material subjected to thermal desorption produced distinctly different GCMS chromatograms at each temperature, containing fractions of both low and high chromatographic mobility. The relative amounts of detectable volatiles released at each temperature also differed, with type II kerogen and cyanide polymer containing the highest percentage of low-temperature components. In all the samples, the highest yield of released compounds occurred at 300 C. Only cyanide polymer evolved a homologous hydrocarbon series, suggesting that it is the only material among those examined that contains a truly polymeric structure. Pyrolysis/gas chromatography/mass spectrometry has been used extensively for analysis of terrestrial organic macromolecular materials, and was also part of the instrument package on the Viking landers. Thorough analysis by pyrolysis usually employs temperatures of 500 C or higher, which for in situ analyses can be problematic given spacecraft power and materials constraints. This study demonstrates that heating of organic materials of astrobiological relevance to temperatures as low as 200-300 C for short periods releases volatile components that can be analyzed by gas chromatography and mass spectrometry. Even in the absence of full pyrolysis, useful chemical information on samples can be obtained, and materials from different biological and abiological sources can be distinguished. The research described in this paper was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration.

Facial Regioselective Synthesis of Novel Bioactive Spiropyrrolidine/Pyrrolizine-Oxindole Derivatives via a Three Components Reaction as Potential Antimicrobial Agents.

PubMed

Hassaneen, Huwaida M E; Eid, Elshimaa M; Eid, Hamid A; Farghaly, Thoraya A; Mabkhot, Yahia Nasser

2017-02-26

This article presents the synthesis of new derivatives of spirooxindole-spiropiperidinone- pyrrolidines 6a - j and spirooxindole-spiropiperidinone-pyrrolizines 8a - j, through a 1,3-dipolar cycloaddition reaction of azomethineylides generated from isatin, sarcosine, and l-proline, through a decarboxylative route with dipolarophile 4a - j . All of the newly synthesized compounds were evaluated for their antimicrobial activities and their minimum inhibitory concentration (MIC) against most of the test organisms. The tested compounds displayed excellent activity against all of the tested microorganisms.

A Systems Approach to Assessing Risk: The Role of Metabolism Research in Describing and Predicting Exposure

EPA Science Inventory

An important component of assessing risk is defining the exposure of a chemical stressor to a target organism. Often the chemical stressor is assumed to be a single compound even when it is comprised of different stereoisomers (e.g., pyrethroids and 1,2,4-triazole fungicides), w...

Edwin M. McMillan

Science.gov Websites

mixture. The separation of the different components in these compound earths has been no easy task, since terbium and dysprosium in the lanthanides. By irradiating different sorts of heavy atoms with neutrons Berkeley Lab Search Submit Web People Close About the Lab Leadership/Organization Calendar News Center

A Fluorogenic Aromatic Nucleophilic Substitution Reaction for Demonstrating Normal-Phase Chromatography and Isolation of Nitrobenzoxadiazole Chromophores

ERIC Educational Resources Information Center

Key, Jessie A.; Li, Matthew D.; Cairo, Christopher W.

2011-01-01

Normal-phase chromatography is an essential technique for monitoring chemical reactions, identifying the presence of specific components, as well as the purification of organic compounds. An experiment to facilitate the instruction and understanding of the concepts behind normal-phase chromatography at the introductory and intermediate…

Characterization of Regional Marginal Abatement Cost Curves for NOx that Incorporate Control Measures, Renewable Energy, Energy Efficiency and Fuel Switching

EPA Science Inventory

Anthropogenic nitrogen oxides (NOx) are emitted when fossil fuels are combusted. In the atmosphere, NOx reacts with volatile organic compounds (VOCs) to produce tropospheric ozone, a component of photochemical smog. In most parts of the country, strategies for reducing ozone gene...

A PHYSIOLOGICALLY-BASED PHARMACOKINETIC MODEL FOR TOLUENE IN THE LONG EVANS RAT: BODY COMPOSITION AND PHYSICAL ACTIVITY.

EPA Science Inventory

A physiologically-based pharmacokinetic (PBPK) model for inhaled toluene was developed for Long-Evans rats as a component of an exposure-dose-response (EDR) model for volatile organic compounds. The PBPK model was needed to link airborne toluene exposure to its concentration in b...

Emission Rates of Volatile Organic Compounds Released from Newly Produced Household Furniture Products Using a Large-Scale Chamber Testing Method

PubMed Central

Ho, Duy Xuan; Kim, Ki-Hyun; Ryeul Sohn, Jong; Hee Oh, Youn; Ahn, Ji-Won

2011-01-01

The emission rates of volatile organic compounds (VOCs) were measured to investigate the emission characteristics of five types of common furniture products using a 5 m3 size chamber at 25°C and 50% humidity. The results indicated that toluene and α-pinene are the most dominant components. The emission rates of individual components decreased constantly through time, approaching the equilibrium emission level. The relative ordering of their emission rates, if assessed in terms of total VOC (TVOC), can be arranged as follows: dining table > sofa > desk chair > bedside table > cabinet. If the emission rates of VOCs are examined between different chemical groups, they can also be arranged in the following order: aromatic (AR) > terpenes (TER) > carbonyl (CBN) > others > paraffin (PR) > olefin (HOL) > halogenated paraffin (HPR). In addition, if emission strengths are compared between coated and uncoated furniture, there is no significant difference in terms of emission magnitude. Our results indicate that the emission characteristics of VOC are greatly distinguished between different furniture products in terms of relative dominance between different chemicals. PMID:22125421

Characterization of organic and conventional sweet basil leaves using chromatographic and flow-injection mass spectrometric (FIMS) fingerprints combined with principal component analysis

PubMed Central

Lu, Yingjian; Gao, Boyan; Chen, Pei; Charles, Denys; Yu, Liangli (Lucy)

2014-01-01

Sweet basil, Ocimum basilicum., is one of the most important and wildly used spices and has been shown to have antioxidant, antibacterial, and anti-diarrheal activities. In this study, high performance liquid chromatographic (HPLC) and flow-injection mass spectrometric (FIMS) fingerprinting techniques were used to differentiate organic and conventional sweet basil leaf samples. Principal component analysis (PCA) of the fingerprints indicated that both HPLC and FIMS fingerprints could effectively detect the chemical differences in the organic and conventional sweet basil leaf samples. This study suggested that the organic basil sample contained greater concentrations of almost all the major compounds than its conventional counterpart on a per same botanical weight basis. The FIMS method was able to rapidly differentiate the organic and conventional sweet basil leaf samples (1 min analysis time), whereas the HPLC fingerprints provided more information about the chemical composition of the basil samples with a longer analytical time. PMID:24518341

Characterisation of organic and conventional sweet basil leaves using chromatographic and flow-injection mass spectrometric (FIMS) fingerprints combined with principal component analysis.

PubMed

Lu, Yingjian; Gao, Boyan; Chen, Pei; Charles, Denys; Yu, Liangli Lucy

2014-07-01

Sweet basil, Ocimum basilicum, is one of the most important and wildly used spices and has been shown to have antioxidant, antibacterial, and anti-diarrheal activities. In this study, high performance liquid chromatographic (HPLC) and flow-injection mass spectrometric (FIMS) fingerprinting techniques were used to differentiate organic and conventional sweet basil leaf samples. Principal component analysis (PCA) of the fingerprints indicated that both HPLC and FIMS fingerprints could effectively detect the chemical differences in the organic and conventional sweet basil leaf samples. This study suggested that the organic basil sample contained greater concentrations of almost all the major compounds than its conventional counterpart on a per same botanical weight basis. The FIMS method was able to rapidly differentiate the organic and conventional sweet basil leaf samples (1min analysis time), whereas the HPLC fingerprints provided more information about the chemical composition of the basil samples with a longer analytical time. Copyright © 2014 Elsevier Ltd. All rights reserved.

Volatile compounds of sulfur in the Fe-C-S system at 5.3 GPa and 1300°C

NASA Astrophysics Data System (ADS)

Zhimulev, E. I.; Sonin, V. M.; Bul'bak, T. A.; Chepurov, A. I.; Tomilenko, A. A.; Pokhilenko, N. P.

2015-05-01

This report presents the results of experimental studies of the fluid phase in the Fe-C-S system at high P and T values (5.3 GPa and 1300°C) conforming to diamond synthesis. The samples for experiments were mounted on air; therefore, the volatile compounds detected after the experiments are characterized by a wide variety and complicated composition involving both inorganic and organic components. Among the inorganic compounds, CO2, H2O, N2, SO2, CS2, and COS were detected. The GC/MS analysis revealed hydrocarbons (paraffins, olefins, and arenes), including high-molecular compounds. The formation of heavy hydrocarbons confirms their thermodynamic stability under high pressure. Oxygenated hydrocarbons (alcohols, aldehydes, ketones, carboxylic acids, and ethers) were also detected.

Water-Rock Reactions on Non-Planetary Bodies in the Early Solar System

NASA Astrophysics Data System (ADS)

Zolotov, M. Y.

2005-12-01

Reactions of aqueous fluids with rocks shortly after formation of the solar system affected the oxidation states, mineralogy, organic speciation, ice composition, and surface/atmospheric chemistry of asteroids, icy satellites of giant plants, and possibly Kuiper belt objects. Water condensed as ice in the solar nebula, was incorporated into the composition of these bodies together with rocky components represented by extremely reduced and anhydrous nebular condensates (e.g., Fe-rich metal, forsterite, low-Ca pyroxene, troilite, Ca-Mg-Al oxides, phosphides), presolar grains (SiC, graphite, diamond, Al-, Mg-, Ti-oxides) and organic compounds and polymers. Radioactive decay of short-lived radionuclides on small bodies, and accretionary heat and decay of long-lived radionuclides on large bodies provided energy to melt ice. On smaller bodies, low gravity precluded separation of water from rocks and restricted fluid dynamics. On larger bodies, water was separated from descending rocks, limiting the duration of water-rock reactions. Competitive oxidation and hydration by water affected both inorganic and organic compounds in rocks. Oxidation of minerals led to formation of ferrous silicates, magnetite, pyrrhotite, Ni sulfides, Ni-rich metal alloys, chromite, phosphates, carbonates and sulfates. Hydration caused formation of phyllosilicates (serpentine, chlorites, smectite clays, amphiboles, and micas), hydroxides, and hydrated sulfides and salts. High water/rock ratios, elevated temperatures and low pressures favored oxidation. Low temperatures supported hydration. In some icy satellites (Europa, Ganymede) high water content and hydrothermal processes during differentiation may have caused profound oxidation leading to carbonates and even sulfates. Since water was the only early oxidizing agent, the elevated oxidation state of Io implies its early aqueous history. Hydrogen was produced in all oxidation reactions and preferentially separated into the gas phase. Escape of H2 into space promoted oxidation, consistent with the high oxidation state of highly porous CI and CM carbonaceous chondrites. Low porosity and permeability, filling of pore space with secondary minerals, and sealing of outer zones with ice restricted H2 escape, retarded some oxidation reactions and caused incomplete reduction of minerals formed earlier by oxidation. For example, magnetite was partially converted to ferrous silicates. The limited oxidation and signs of reduction in some meteorite types (unequilibrated ordinary and CV3 carbonaceous chondrites) is consistent with low amounts of incorporated water ice and low porosity of parent asteroids. Although prolonged heating of bodies caused dehydration and some reduction, water-rock reactions led to net oxidation of primary rocky components, consistent with the elevated oxidation states of metamorphosed chondrites and Io. Interaction of water with organic compounds and carbon grains caused disproportionation of carbon leading to O-bearing organic compounds and CO2, as well as to hydrogenated organic compounds and methane. In small bodies, organic matter was only partially altered. In some icy satellites, prolonged reactions and elevated pressures favored formation of light hydrocarbons and methane, consistent with observations (e.g., Titan, Triton). In most bodies, net oxidation of organic compounds can be attributed to preservation of CO2 and O-bearing organics in solution, ices and carbonates, and escape of H2 formed through oxidation reactions.

Volatile Organic Compounds: Characteristics, distribution and sources in urban schools

NASA Astrophysics Data System (ADS)

Mishra, Nitika; Bartsch, Jennifer; Ayoko, Godwin A.; Salthammer, Tunga; Morawska, Lidia

2015-04-01

Long term exposure to organic pollutants, both inside and outside school buildings may affect children's health and influence their learning performance. Since children spend significant amount of time in school, air quality, especially in classrooms plays a key role in determining the health risks associated with exposure at schools. Within this context, the present study investigated the ambient concentrations of Volatile Organic Compounds (VOCs) in 25 primary schools in Brisbane with the aim to quantify the indoor and outdoor VOCs concentrations, identify VOCs sources and their contribution, and based on these; propose mitigation measures to reduce VOCs exposure in schools. One of the most important findings is the occurrence of indoor sources, indicated by the I/O ratio >1 in 19 schools. Principal Component Analysis with Varimax rotation was used to identify common sources of VOCs and source contribution was calculated using an Absolute Principal Component Scores technique. The result showed that outdoor 47% of VOCs were contributed by petrol vehicle exhaust but the overall cleaning products had the highest contribution of 41% indoors followed by air fresheners and art and craft activities. These findings point to the need for a range of basic precautions during the selection, use and storage of cleaning products and materials to reduce the risk from these sources.

Ecological Relationships Between Components in Closed Aquatic Ecosystems

NASA Astrophysics Data System (ADS)

Pisman, Tamara; Somova, Lydia

The work considers the problems of relationships between algae and other microorganisms in aquatic ecosystems. Using small-scale laboratory "autotroph-heterotroph" ecosystems with different types of closure, we showed the results of the investigation into the ecological relation-ships of algae in biocenoses. The autotrophic component was represented by green microalgae, and the heterotrophic component -by yeast and bacteria. An important role in functioning of algobacterial communities is played by 2 -2 (oxygen -carbon dioxide) exchange. The gas exchange between algae and yeast was studied in the "autotroph-heterotroph" gas-closed ecosystem with space-divided components. It was shown that the gas exchange closure of the components into a system prolongs its existence. Hav-ing increased the degree of the system closure by introducing two yeast species with positive metabolic interaction to the heterotrophic component, we observed a significant increase in the gas exchange between the components and thus in the biomass of algae and yeast. The most ancient and ecologically relevant symbioses known in nature are symbiotic associa-tions of algae and heterotrophic organisms. The main symbionts of algae in aquatic ecosystems are bacteria. The cenosis-forming role of algae is based on two characteristics: firstly, their mucous covers and membranes are able to absorb and retain large amounts of water; secondly, many algae evolve various organic substances during their lifetime. An example of algobacterial associations are microalgae Chlorella vulgaris and accompanying microbial flora. Experiments with non-sterile batch culture of algae showed that the increase in the algae biomass was accompanied by the increase in the bacterial biomass. As a result of theoretical and experi-mental investigation into their relationships, it was shown that the largest biomass of bacteria is achieved when using organic substances evolved by algae and having bacteria grow on dead algae; i.e. bacteria can also act as decomposers. It was demonstrated that the cenosis-forming role of algae and bacteria in an algobacterial cenosis is determined by accumulation of both organic matter and nitrogen which is included into the cycle of matter. Thus, the process of C-compound evolution by algae in an algobacterial cenosis is strongly connected with the process of consumption of these compounds by corresponding bacteria, which, in their turn, ensure photosynthesis and algae development by evolving 2 and nitrogen.

The provenance, formation, and implications of reduced carbon phases in Martian meteorites

NASA Astrophysics Data System (ADS)

Steele, Andrew; McCubbin, Francis M.; Fries, Marc D.

2016-11-01

This review is intended to summarize the current observations of reduced carbon in Martian meteorites, differentiating between terrestrial contamination and carbon that is indigenous to Mars. Indeed, the identification of Martian organic matter is among the highest priority targets for robotic spacecraft missions in the next decade, including the Mars Science Laboratory and Mars 2020. Organic carbon compounds are essential building blocks of terrestrial life, so the occurrence and origin (biotic or abiotic) of organic compounds on Mars is of great significance; however, not all forms of reduced carbon are conducive to biological systems. This paper discusses the significance of reduced organic carbon (including methane) in Martian geological and astrobiological systems. Specifically, it summarizes current thinking on the nature, sources, and sinks of Martian organic carbon, a key component to Martian habitability. Based on this compilation, reduced organic carbon on Mars, including detections of methane in the Martian atmosphere, is best described through a combination of abiotic organic synthesis on Mars and infall of extraterrestrial carbonaceous material. Although conclusive signs of Martian life have yet to be revealed, we have developed a strategy for life detection on Mars that can be utilized in future life-detection studies.

Functional Coupling of Human Microphysiology Systems: Intestine, Liver, Kidney Proximal Tubule, Blood-Brain Barrier and Skeletal Muscle

PubMed Central

Vernetti, Lawrence; Gough, Albert; Baetz, Nicholas; Blutt, Sarah; Broughman, James R.; Brown, Jacquelyn A.; Foulke-Abel, Jennifer; Hasan, Nesrin; In, Julie; Kelly, Edward; Kovbasnjuk, Olga; Repper, Jonathan; Senutovitch, Nina; Stabb, Janet; Yeung, Catherine; Zachos, Nick C.; Donowitz, Mark; Estes, Mary; Himmelfarb, Jonathan; Truskey, George; Wikswo, John P.; Taylor, D. Lansing

2017-01-01

Organ interactions resulting from drug, metabolite or xenobiotic transport between organs are key components of human metabolism that impact therapeutic action and toxic side effects. Preclinical animal testing often fails to predict adverse outcomes arising from sequential, multi-organ metabolism of drugs and xenobiotics. Human microphysiological systems (MPS) can model these interactions and are predicted to dramatically improve the efficiency of the drug development process. In this study, five human MPS models were evaluated for functional coupling, defined as the determination of organ interactions via an in vivo-like sequential, organ-to-organ transfer of media. MPS models representing the major absorption, metabolism and clearance organs (the jejunum, liver and kidney) were evaluated, along with skeletal muscle and neurovascular models. Three compounds were evaluated for organ-specific processing: terfenadine for pharmacokinetics (PK) and toxicity; trimethylamine (TMA) as a potentially toxic microbiome metabolite; and vitamin D3. We show that the organ-specific processing of these compounds was consistent with clinical data, and discovered that trimethylamine-N-oxide (TMAO) crosses the blood-brain barrier. These studies demonstrate the potential of human MPS for multi-organ toxicity and absorption, distribution, metabolism and excretion (ADME), provide guidance for physically coupling MPS, and offer an approach to coupling MPS with distinct media and perfusion requirements. PMID:28176881

Identifying sources of emerging organic contaminants in a mixed use watershed using principal components analysis.

PubMed

Karpuzcu, M Ekrem; Fairbairn, David; Arnold, William A; Barber, Brian L; Kaufenberg, Elizabeth; Koskinen, William C; Novak, Paige J; Rice, Pamela J; Swackhamer, Deborah L

2014-01-01

Principal components analysis (PCA) was used to identify sources of emerging organic contaminants in the Zumbro River watershed in Southeastern Minnesota. Two main principal components (PCs) were identified, which together explained more than 50% of the variance in the data. Principal Component 1 (PC1) was attributed to urban wastewater-derived sources, including municipal wastewater and residential septic tank effluents, while Principal Component 2 (PC2) was attributed to agricultural sources. The variances of the concentrations of cotinine, DEET and the prescription drugs carbamazepine, erythromycin and sulfamethoxazole were best explained by PC1, while the variances of the concentrations of the agricultural pesticides atrazine, metolachlor and acetochlor were best explained by PC2. Mixed use compounds carbaryl, iprodione and daidzein did not specifically group with either PC1 or PC2. Furthermore, despite the fact that caffeine and acetaminophen have been historically associated with human use, they could not be attributed to a single dominant land use category (e.g., urban/residential or agricultural). Contributions from septic systems did not clarify the source for these two compounds, suggesting that additional sources, such as runoff from biosolid-amended soils, may exist. Based on these results, PCA may be a useful way to broadly categorize the sources of new and previously uncharacterized emerging contaminants or may help to clarify transport pathways in a given area. Acetaminophen and caffeine were not ideal markers for urban/residential contamination sources in the study area and may need to be reconsidered as such in other areas as well.

Some final conclusions and supporting experiments related to the search for organic compounds on the surface of Mars

NASA Technical Reports Server (NTRS)

Biemann, K.; Lavoie, J. M., Jr.

1979-01-01

The Viking molecular analysis experiment has demonstrated the absence (within the detection limits which range from levels of parts per million to below parts per billion) of organic substances in the Martian surface soil at the two Viking landing sites. Laboratory experiments with sterile and nonsterile antarctic samples further demonstrate the capability and reliability of the instrument. The circumstances under which organic components could have escaped detection, such as inaccessibility or extreme thermal stability of organic polymers, are discussed but are found to be unlikely. The inability of the instrument to detect free oxygen evolved from soil samples is pointed out.

Seasonal changes of concentrations of inorganic and organic nitrogen in coastal marine sediments

NASA Astrophysics Data System (ADS)

Yamada, Hisashi; Kayama, Mitsu; Fujisawa, Kuniyasu

1987-05-01

The seasonal fluctuations of the concentration of nitrogenous compounds in sediments was investigated for three regions of the Seto Inland Sea in Japan; the variation of nitrogenous compounds in sediments was also studied in a laboratory experiment. The amounts of ammonium, dissolved organic nitrogen, nitrite and nitrate, as percentages of the dissolved total nitrogen of the interstitial water, were in the ranges of 47-99%, 10-50%, 0·1-0·6% and 0·3-4·1%, respectively. Ammonium was the major component and organic nitrogen was the next most important. The concentrations of these nitrogenous compounds changed seasonally: dissolved total nitrogen was higher in the warm month of September than in May; ammonium increased in warm months and decreased in cold months, but nitrite and nitrate increased in cold months. It was possible to explain the seasonal fluctuation of nitrogenous compounds in terms of the rates of the metabolic pathways of nitrogen in the sediments. Ammonium was not necessarily correlated with dissolved organic nitrogen. From this, it was considered that ammonium did not occur from solubilization of particulate organic nitrogen followed by mineralization, but from direct mineralization of particulate organic nitrogen in sediments. For the sediments of Suho Nada, Hiuchi Nada and station B-47 in Beppu Bay, the ratio of dissolved ammonium to adsorbed ammonium in the sediments was in the range 10-25%, but the ratio was 60-70% of adsorbed ammonium in the considerably anaerobic sediments at station B-45 in Beppu Bay. The ratio of dissolved ammonium to adsorbed ammonium increased with the increase of the concentration of sulfide in sediments. It was recognized that the anaerobic conditions of the sediments led to the dissolution of adsorbed ammonium.

Toxic organic substances and marker compounds in size-segregated urban particulate matter - Implications for involvement in the in vitro bioactivity of the extractable organic matter.

PubMed

Besis, Athanasios; Tsolakidou, Alexandra; Balla, Dimitra; Samara, Constantini; Voutsa, Dimitra; Pantazaki, Anastasia; Choli-Papadopoulou, Theodora; Lialiaris, Theodore S

2017-11-01

Toxic organic substances and polar organic marker compounds, i.e. polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs) and their nitro-derivatives (N-PAHs), as well as dicarboxylic acids (DCAs) and sugars/sugar anhydrites (S/SAs) were analyzed in size-segregated PM samples (<0.49, 0.49-0.97, 0.97-3 and >3 μm) collected at two urban sites (urban traffic and urban background) during the cold and the warm season. The potential associations between the organic PM determinants and the adverse cellular effects (i.e. cytotoxicity, genotoxicity, DNA damage, oxidative DNA adduct formation, and inflammatory response) induced by the extractable organic matter (EOM) of PM, previously measured in Velali et al. (2016b), were investigated by bivariate correlations and Principal Component Analysis (PCA). Partial Least Square regression analysis (PLS) was also employed in order to identify the chemical classes mainly involved in the EOM-induced toxicological endpoints in the various particle size fractions. Results indicated that particle size range <0.49 μm was the major carrier of PM mass and organic compounds at both sites. All toxic organic compounds exhibited higher concentrations at the urban traffic site, except PCBs and OCPs that did not exhibit intra-urban variations. Conversely, wintertime levels of levoglucosan were significantly higher at the urban background site as a result of residential biomass burning. The PLS regression analysis allowed quite good prediction of the EOM-induced cytotoxicity and genotoxicity based on the determined organic chemical classes, particularly for the finest size fraction of PM. Nevertheless, it is expected that other chemical constituents, not determined here, also contribute to the measured toxicological responses. Copyright © 2017. Published by Elsevier Ltd.

Volatile organic compounds associated with Plasmodium falciparum infection in vitro.

PubMed

Correa, Ricardo; Coronado, Lorena M; Garrido, Anette C; Durant-Archibold, Armando A; Spadafora, Carmenza

2017-05-02

In order to identify new ways to prevent transmission of vector-borne diseases such as malaria, efforts have been made to understand how insects are attracted to humans. Vector-host interaction studies have shown that several volatile compounds play an important role in attracting mosquitoes to human targets. A headspace solid-phase micro-extraction/gas chromatography-mass spectrometry (HSPME GC-MS) analysis of the volatile organic composition of extracellular vesicles (EVs) and supernatants of ultracentrifugation (SNUs) was carried out in Plasmodium falciparum-infected cultures with high and low parasitemias. A list of 18 volatile organic compounds (VOCs) was obtained from the EVs of both infected and uninfected RBCs with 1,2,3-Propanetriol, diacetate (diacetin) increased in the infected EVs, regardless of the parasitemia of the culture. The supernatant analysis, however, gave off 56 VOCs, with pentane 2,2,4-trimethyl being present in all the SNUs of uninfected erythrocytes but absent from the parasite-infected ones. Standing out in this study was hexanal, a reported insect attractant, which was the only VOC present in all samples from SNUs from infected erythrocytes and absent from uninfected ones, suggesting that it originates during parasite infection. The hexanal compound, reportedly a low-level component found in healthy human samples such as breath and plasma, had not been found in previous analyses of P. falciparum-infected patients or cultures. This compound has been reported as an Anopheles gambiae attractant in plants. While the compound could be produced during infection by the malaria parasite in human erythrocytes, the A. gambiae attraction could be used by the parasite as a strategy for transmission.

Measurements of volatile organic compounds emitted from plants in the metropolitan area of São Paulo City , Brazil.

NASA Astrophysics Data System (ADS)

Carvalho, L.; Pisani, S.; Pool, C.; Vasconcellos, P.

2003-04-01

The presence of the biogenic hydrocarbons in an NO_x-containing atmosphere can enhance ozone generation and the impact of volatile organic compounds (VOCs) emitted from vegetation on atmospheric chemistry has been investigated. No study of VOC emission rates from plant species has been carried out in São Paulo City, Brazil, prior to this work. This study is part of a three-years project on biogenic volatile organic compounds emissions from species of plants found in the vegetation of the São Paulo metropolitan area. Typical plants (Alchornea sidifolia, Cupania oblongifolia, Cecropia pachystachia, Casearia sylvestris, Machaerium villosum, Croton floribundus, Myrcia rostrata, Solanum erianthum and Ficus insípida) were selected and identical species were studied in urban, sub-urban and forest regions. Biogenic hydrocarbons were determined placing branches of plants in enclosures and measuring the accumulation of emitted compounds in an all-Teflon chamber, the cuvette system. Measuring ambient VOC concentration adsorptive preconcentration, followed by GC-MS after thermal desorption of the sample, was employed to determine components heavier than C_5. Collection of carbonyl compounds on 2, 4-dinitrophenylhydrazine coated particles followed by HPLC-UV was used to analyze low molecular weight carbonyl compounds. Emissions rates of isoprene, a-pinene, camphene and limonene ranged from 0.01 to 2.16 μg C/h.g and emissions rates of aldehydes (C_1 - C_6), acrolein, methacrolein, 2-butanone and acetone ranged from 0.04 to 4.20 μg C/h.g. Ambient and chamber temperatures, relative humidity, light intensity, O_3 and NO_x were monitored during experiments.

Carbonaceous Components in the Comet Halley Dust

NASA Technical Reports Server (NTRS)

Fomenkova, M. N.; Chang, S.; Mukhin, L. M.

1994-01-01

Cometary grains containing large amounts of carbon and/or organic matter (CHON) were discovered by in situ measurements of comet Halley dust composition during VEGA and GIOTTO flyby missions. In this paper, we report the classification of these cometary, grains by means of cluster analysis, discuss the resulting compositional groups, and compare them with substances observed or hypothesized in meteorites, interplanetary dust particles, and the interstellar medium. Grains dominated by carbon and/or organic matter (CHON grains) represent approx. 22% of the total population of measured cometary dust particles. They, usually contain a minor abundance of rock-forming elements as well. Grains having organic material are relatively more abundant in the vicinity of the nucleus than in the outer regions of the coma, which suggests decomposition of the organics in the coma environment. The majority of comet Halley organic particles are multicomponent mixtures of carbon phases and organic compounds. Possibly, the cometary CHON grains may be related to kerogen material of an interstellar origin in carbonaceous meteorites. Pure carbon grains, hydrocarbons and polymers of cyanopolyynes, and multi-carbon monoxides are present in cometary dust as compositionally simple and distinctive components among a variety of others. There is no clear evidence of significant presence of pure formaldehyde or HCN polymers in Halley dust particles. The diversity of types of cometary organic compounds is consistent with the inter-stellar dust model of comets and probably reflects differences in composition of precursor dust. Preservation of this heterogeneity among submicron particles suggest the gentle formation of cometary, nucleus by aggregation of interstellar dust in the protosolar nebula without complete mixing or chemical homogenization at the submicron level.

Flow-through pretreatment of lignocellulosic biomass with inorganic nanoporous membranes

DOEpatents

Bhave, Ramesh R.; Lynd, Lee; Shao, Xiongjun

2018-04-03

A process for the pretreatment of lignocellulosic biomass is provided. The process generally includes flowing water through a pretreatment reactor containing a bed of particulate ligno-cellulosic biomass to produce a pressurized, high-temperature hydrolyzate exit stream, separating solubilized compounds from the hydrolyzate exit stream using an inorganic nanoporous membrane element, fractionating the retentate enriched in solubilized organic components and recycling the permeate to the pretreatment reactor. The pretreatment process provides solubilized organics in concentrated form for the subsequent conversion into biofuels and other chemicals.

Hydrophilic interaction liquid chromatography in the speciation analysis of selenium.

PubMed

Sentkowska, Aleksandra; Pyrzynska, Krystyna

2018-02-01

The hydrophilic interaction liquid chromatography (HILIC) coupled to mass spectrometry was employed to study retention behavior of selected selenium compounds using two different HILIC stationary phases: silica and zwitterionic. Two organic solvents - acetonitrile and methanol - were compared as a component of mobile phase. Separation parameters such as a content of organic modifier, the eluent pH and inorganic buffer concentration were investigated. Based on all observations, methanol seems to be beneficial for the separation of studied compounds. The optimal HILIC separation method involved silica column and eluent composed of 85% MeOH and CH 3 COONH 4 (8 mM, pH 7) was compared to RP method in terms of time of the single run, the separation efficiency and limit of detection. Copyright © 2018 Elsevier B.V. All rights reserved.

The scent of disease: volatile organic compounds of the human body related to disease and disorder.

PubMed

Shirasu, Mika; Touhara, Kazushige

2011-09-01

Hundreds of volatile organic compounds (VOCs) are emitted from the human body, and the components of VOCs usually reflect the metabolic condition of an individual. Therefore, contracting an infectious or metabolic disease often results in a change in body odour. Recent progresses in analytical techniques allow rapid analyses of VOCs derived from breath, blood, skin and urine. Disease-specific VOCs can be used as diagnostic olfactory biomarkers of infectious diseases, metabolic diseases, genetic disorders and other kinds of diseases. Elucidation of pathophysiological mechanisms underlying production of disease-specific VOCs may provide novel insights into therapeutic approaches for treatments for various diseases. This review summarizes the current knowledge on chemical and clinical aspects of body-derived VOCs, and provides a brief outlook at the future of olfactory diagnosis.

Influence of frontal zones on the distribution of particulate matter and organic compounds in surface waters of the Atlantic and Southern Oceans

NASA Astrophysics Data System (ADS)

Nemirovskaya, I. A.; Lisitzin, A. P.; Kravchishina, M. D.; Redzhepova, Z. Yu.

2015-10-01

Particulate matter and organic compounds (chlorophyll, lipids, and hydrocarbons) were analyzed in surface waters along the routes of R/Vs Akademik Fedorov (cruise 32) and Akademik Treshnikov (cruise 2) in February-May of 2012 and 2014, respectively, in the course of the 57th and 59th Russian Antarctic expeditions. It was found that the frontal zones exert the primary influence on the concentrations of the mentioned components in the Southern Ocean and in the western part of the Atlantic Ocean. The supply of pollutants into the Eastern Atlantic Ocean on the shelf of the Iberian peninsula results in a pronounced increase in the concentrations of lipids and hydrocarbons causing local anthropogenic pollution zones.

A hydrophobic organelle probe based on aggregation-induced emission: Nanosuspension preparation and direct use for endoplasmic reticulum imaging in living cells

NASA Astrophysics Data System (ADS)

Zheng, Sichao; Huang, Cuihong; Zhao, Xuyan; Zhang, Yong; Liu, Shuwen; Zhu, Qiuhua

2018-01-01

Organic fluorophores have a wide range of biological uses and are usually needed to be prepared as water-soluble compounds or nanoparticles for applications in aqueous biosystems owing to their hydrophobic properties, which often is a complex, time-consuming and high-cost process. Here, the nanoparticle preparation of hydrophobic fluorophores and their application in cell imaging have been investigated. It was found: a) fetal bovine serum (FBS) shows an excellent dispersion effect on hydrophobic small-molecule organic compounds; b) a hydrophobic C6-unsubstituted tetrahydropyrimidine (Me-THP-Naph) can be prepared as nanosuspensions utilizing cell culture medium with 10% FBS and directly be used as a specific real-time imaging probe for the endoplasmic reticulum (ER), a dynamic organelle playing a crucial role in many cellular processes. Compared with existing ER-targeted organic fluorescent probes, Me-THP-Naph, a product of an efficient five-component reaction that we developed, has unconventional aggregation-induced emission characteristics and shows advantages of low cost, long-term staining, good photostability, high signal-to-noise ratio and excellent biocompatibility, which make it a potential specific probe for real-time ER imaging. More importantly, this work affords a simple strategy for direct application of hydrophobic organic compounds in aqueous biological systems.

Real-time analysis of organic compounds in ship engine aerosol emissions using resonance-enhanced multiphoton ionisation and proton transfer mass spectrometry.

PubMed

Radischat, Christian; Sippula, Olli; Stengel, Benjamin; Klingbeil, Sophie; Sklorz, Martin; Rabe, Rom; Streibel, Thorsten; Harndorf, Horst; Zimmermann, Ralf

2015-08-01

Organic combustion aerosols from a marine medium-speed diesel engine, capable to run on distillate (diesel fuel) and residual fuels (heavy fuel oil), were investigated under various operating conditions and engine parameters. The online chemical characterisation of the organic components was conducted using a resonance-enhanced multiphoton ionisation time-of-flight mass spectrometer (REMPI TOF MS) and a proton transfer reaction-quadrupole mass spectrometer (PTR-QMS). Oxygenated species, alkenes and aromatic hydrocarbons were characterised. Especially the aromatic hydrocarbons and their alkylated derivatives were very prominent in the exhaust of both fuels. Emission factors of known health-hazardous compounds (e.g. mono- and poly-aromatic hydrocarbons) were calculated and found in higher amounts for heavy fuel oil (HFO) at typical engine loadings. Lower engine loads lead in general to increasing emissions for both fuels for almost every compound, e.g. naphthalene emissions varied for diesel fuel exhaust between 0.7 mg/kWh (75 % engine load, late start of injection (SOI)) and 11.8 mg/kWh (10 % engine load, late SOI) and for HFO exhaust between 3.3 and 60.5 mg/kWh, respectively. Both used mass spectrometric techniques showed that they are particularly suitable methods for online monitoring of combustion compounds and very helpful for the characterisation of health-relevant substances. Graphical abstract Three-dimensional REMPI data of organic species in diesel fuel and heavy fuel oil exhaust.

Tight coupling of particle size and composition in atmospheric cloud droplet activation

NASA Astrophysics Data System (ADS)

Topping, D.; McFiggans, G.

2011-09-01

The substantial uncertainty in the indirect effect on radiative forcing in large part arises from the influences of atmospheric aerosol particles on (i) the brightness of clouds, exerting significant shortwave cooling with no appreciable compensation in the longwave, and on (ii) their ability to precipitate, with implications for cloud cover and lifetime. Predicting the ambient conditions at which aerosol particles may become cloud droplets is largely reliant on an equilibrium relationship derived in 1936. However, the theoretical basis of the relationship restricts its application to particles solely comprising involatile compounds and water, whereas a substantial fraction of particles in the real atmosphere will contain potentially thousands of semi-volatile organic compounds in addition to containing semi-volatile inorganic components such as ammonium nitrate. We show that equilibration of atmospherically reasonable concentrations of organic compounds with a growing particle as the ambient humidity increases has larger implications on cloud droplet formation than any other equilibrium compositional dependence, owing to inextricable linkage between the aerosol composition and a particles size under ambient conditions. Whilst previous attempts to account for co-condensation of gases other than water vapour have been restricted to one inorganic condensate, our method demonstrates that accounting for the co-condensation of any number of organic compounds substantially decreases the saturation ratio of water vapour required for droplet activation. This effect is far greater than any other compositional dependence; moreso even than the unphysical effect of surface tension reduction in aqueous organic mixtures, ignoring differences in bulk and surface surfactant concentrations.

Probing Complex Free-Radical Reaction Pathways of Fuel Model Compounds

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

Buchanan III, A C; Kidder, Michelle; Beste, Ariana

2012-01-01

Fossil (e.g. coal) and renewable (e.g. woody biomass) organic energy resources have received considerable attention as possible sources of liquid transportation fuels and commodity chemicals. Knowledge of the reactivity of these complex materials has been advanced through fundamental studies of organic compounds that model constituent substructures. In particular, an improved understanding of thermochemical reaction pathways involving free-radical intermediates has arisen from detailed experimental kinetic studies and, more recently, advanced computational investigations. In this presentation, we will discuss our recent investigations of the fundamental pyrolysis pathways of model compounds that represent key substructures in the lignin component of woody biomass withmore » a focus on molecules representative of the dominant beta-O-4 aryl ether linkages. Additional mechanistic insights gleaned from DFT calculations on the kinetics of key elementary reaction steps will also be presented, as well as a few thoughts on the significant contributions of Jim Franz to this area of free radical chemistry.« less

Phytochemical screening, anticancer and antioxidant activities of Origanum vulgare L. ssp. viride (Boiss.) Hayek, a plant of traditional usage.

PubMed

Koldaş, Serkan; Demirtas, Ibrahim; Ozen, Tevfik; Demirci, Mehmet Ali; Behçet, Lütfi

2015-03-15

A detailed phytochemical analysis of Origanum vulgare L. ssp. viride (Boiss.) Hayek was carried out and the antioxidant activities of five different crude extracts were determined. The antiproliferative activities of the extracts were determined using the xCELLigence system (Real Time Cell Analyzer). Differences between the essential oil and volatile organic compound profiles of the plant were shown. The main component of the essential oil was caryophyllene oxide, while the main volatile organic compounds were sabinene and eucalyptol as determined by HS-GC/MS. Phenolic contents of the extracts were determined qualitatively and quantitatively by HPLC/TOF-MS. Ten phenolic compounds were found in the extracts from O. vulgare and Origanum acutidens: rosmarinic acid (in highest abundance), chicoric acid, caffeic acid, p-coumaric acid, gallic acid, quercetin, apigenin-7-glucoside, kaempferol, naringenin and 4-hydroxybenzaldehyde. This study provides first results on the antiproliferative and antioxidant properties and detailed phytochemical screening of O. vulgare ssp. viride (Boiss.) Hayek. © 2014 Society of Chemical Industry.

Effects of polar and nonpolar groups on the solubility of organic compounds in soil organic matter

USGS Publications Warehouse

Chiou, C.T.; Kile, D.E.

1994-01-01

Vapor sorption capacities on a high-organic-content peat, a model for soil organic matter (SOM), were determined at room temperature for the following liquids: n-hexane, 1,4-dioxane, nitroethane, acetone, acetonitrile, 1-propanol, ethanol, and methanol. The linear organic vapor sorption is in keeping with the dominance of vapor partition in peat SOM. These data and similar results of carbon tetrachloride (CT), trichloroethylene (TCE), benzene, ethylene glycol monoethyl ether (EGME), and water on the same peat from earlier studies are used to evaluate the effect of polarity on the vapor partition in SOM. The extrapolated liquid solubility from the vapor isotherm increases sharply from 3-6 wt % for low-polarity liquids (hexane, CT, and benzene) to 62 wt % for polar methanol and correlates positively with the liquid's component solubility parameters for polar interaction (??P) and hydrogen bonding (??h). The same polarity effect may be expected to influence the relative solubilities of a variety of contaminants in SOM and, therefore, the relative deviations between the SOM-water partition coefficients (Kom) and corresponding octanol-water partition coefficients (Kow) for different classes of compounds. The large solubility disparity in SOM between polar and nonpolar solutes suggests that the accurate prediction of Kom from Kow or Sw (solute water solubility) would be limited to compounds of similar polarity.

Development studies of a novel wet oxidation process

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

Rogers, T.W.; Dhooge, P.M.

1995-10-01

Many DOE waste streams and remediates contain complex and variable mixtures of organic compounds, toxic metals, and radionuclides. These materials are often dispersed in organic or inorganic matrices, such as personal protective equipment, various sludges, soils, and water. Incineration and similar combustive processes do not appear to be viable options for treatment of these waste streams due to various considerations. The objective of this project is to develop a novel catalytic wet oxidation process for the treatment of multi-component wastes. The DETOX process uses a unique combination of metal catalysts to increase the rate of oxidation of organic materials.

Thermodynamic Modeling of Organic-Inorganic Aerosols with the Group-Contribution Model AIOMFAC

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Luo, B. P.; Peter, T.

2009-04-01

Liquid aerosol particles are - from a physicochemical viewpoint - mixtures of inorganic salts, acids, water and a large variety of organic compounds (Rogge et al., 1993; Zhang et al., 2007). Molecular interactions between these aerosol components lead to deviations from ideal thermodynamic behavior. Strong non-ideality between organics and dissolved ions may influence the aerosol phases at equilibrium by means of liquid-liquid phase separations into a mainly polar (aqueous) and a less polar (organic) phase. A number of activity models exists to successfully describe the thermodynamic equilibrium of aqueous electrolyte solutions. However, the large number of different, often multi-functional, organic compounds in mixed organic-inorganic particles is a challenging problem for the development of thermodynamic models. The group-contribution concept as introduced in the UNIFAC model by Fredenslund et al. (1975), is a practical method to handle this difficulty and to add a certain predictability for unknown organic substances. We present the group-contribution model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients), which explicitly accounts for molecular interactions between solution constituents, both organic and inorganic, to calculate activities, chemical potentials and the total Gibbs energy of mixed systems (Zuend et al., 2008). This model enables the computation of vapor-liquid (VLE), liquid-liquid (LLE) and solid-liquid (SLE) equilibria within one framework. Focusing on atmospheric applications we considered eight different cations, five anions and a wide range of alcohols/polyols as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are very well represented up to high ionic strength. We show that the semi-empirical middle-range parametrization of direct organic-inorganic interactions in alcohol-water-salt solutions enables accurate computations of vapor-liquid and liquid-liquid equilibria. References Fredenslund, A., Jones, R. L., and Prausnitz, J. M.: Group-Contribution Estimation of Activity Coefficients in Nonideal Liquid Mixtures, AIChE J., 21, 1086-1099, 1975. Rogge, W. F., Mazurek, M. A., Hildemann, L. M., Cass, G. R., and Simoneit, B. R. T.: Quantification of Urban Organic Aerosols at a Molecular Level: Identification, Abundance and Seasonal Variation, Atmos. Environ., 27, 1309-1330, 1993. Zhang, Q. et al.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically influenced Northern Hemisphere midlatitudes, Geophys. Res. Lett., 34, L13 801, 2007. Zuend, A., Marcolli, C., Luo, B. P., and Peter, T.: A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients, Atmos. Chem. Phys., 8, 4559-4593, 2008.

Organic compounds of PM2.5 in Mexico Valley: spatial and temporal patterns, behavior and sources.

PubMed

Amador-Muñoz, O; Villalobos-Pietrini, R; Miranda, J; Vera-Avila, L E

2011-03-15

A longitudinal study on spatial and temporal behavior of particles less than 2.5 μm (PM(2.5)), solvent extracted organic matter (SEOM), polycyclic aromatic hydrocarbons (PAH), n-alkanes and nitro-PAH was carried out for a full year in 2006, at five sites simultaneously around the Metropolitan Zone of Mexico Valley (MZMV). There is rather uniform distribution of PM(2.5) and SEOM in the MZMV regarding gravimetric mass concentration, while some specific organic chemical components showed mass heterogeneity. The highest mass concentrations of target compounds occurred in the dry seasons with respect to the rainy season. Bonfires and fireworks are probably responsible for extreme values of PM(2.5), SEOM and PAH (≥ 228 gmol(-1)). Benzo[ghi]perylene was the most abundant PAH, with C(24)-C(26) the most abundant n-alkanes and 2-nitrofluoranthene and 9-nitroanthracene the most abundant nitro-PAH. The northeast zone was the area with the greatest presence of sources of incomplete diesel combustion, while the central for gasoline combustion. In the southwest, the biogenic sources were more abundant over the anthropogenic sources. This was opposite to the other sites. Factor analysis allowed us to relate different compounds to emitting sources. Three main factors were associated with combustion, pyrolysis and biogenic primary sources while the other factors were associated with secondary organic aerosol formation and industry. Correlation analyses indicated that SEOM originates from different primary emission sources or is formed by different processes than the other variables, except in southwest. Associations among variables suggest that PM(2.5) in the northwest and in the southeast originated mainly from primary emissions or consisted of primary organic compounds. PM(2.5) in the northeast, central and southwest contains a greater proportion of secondary organic compounds, with the less oxidized organic aerosols in the northeast and the most aged organic aerosol in the southwest. This follows the trends in the prevailing wind directions in MZMV during 2006. Copyright © 2010 Elsevier B.V. All rights reserved.

Screening of oil sources by using comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and multivariate statistical analysis.

PubMed

Zhang, Wanfeng; Zhu, Shukui; He, Sheng; Wang, Yanxin

2015-02-06

Using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/TOFMS), volatile and semi-volatile organic compounds in crude oil samples from different reservoirs or regions were analyzed for the development of a molecular fingerprint database. Based on the GC×GC/TOFMS fingerprints of crude oils, principal component analysis (PCA) and cluster analysis were used to distinguish the oil sources and find biomarkers. As a supervised technique, the geological characteristics of crude oils, including thermal maturity, sedimentary environment etc., are assigned to the principal components. The results show that tri-aromatic steroid (TAS) series are the suitable marker compounds in crude oils for the oil screening, and the relative abundances of individual TAS compounds have excellent correlation with oil sources. In order to correct the effects of some other external factors except oil sources, the variables were defined as the content ratio of some target compounds and 13 parameters were proposed for the screening of oil sources. With the developed model, the crude oils were easily discriminated, and the result is in good agreement with the practical geological setting. Copyright © 2014 Elsevier B.V. All rights reserved.

Biochemical constituents of a wild strain of Schizophyllum commune isolated from Achanakmar-Amarkantak Biosphere Reserve (ABR), India.

PubMed

Tripathi, Arpita Mani; Tiwary, Bhupendra N

2013-08-01

A wild strain of Schizophyllum commune (MTCC 9670) isolated from Achanakmar-Amarkantak Biosphere Reserve of Central India was evaluated for the production of bioactive compounds. The chemical constituents of wild and in vitro grown cultures were compared. Under optimized conditions, different organic and aqueous extracts from mycelia and fruiting bodies were used to extract chemical components from the cultures grown in vitro. The gas chromatography combined wih mass spectrometry analysis of extracts identified two phenolic compounds, namely Phenyl benzoate (C13H10O2) and 4-(phenyl methoxy) phenol (C13H12O2) in the ethanolic extract of in vitro grown fruiting bodies and one antibacterial compound Pyrrolo (1, 2-a) piperazine-3, 6-dione (C7H10O2N2) in the methanolic extract of mycelia. High-performance liquid chromatography analysis revealed that the gallic acid and L-ascorbic acid were identifiable antioxidant components in the extracts possessing high free radical scavenging activity. The findings suggest that the wild strain of S. commune may serve as the source of novel bioactive compounds with effective antimicrobial and antioxidant activities.

Clathrate formation and phase equilibria in the thiourea-bromoform system

NASA Astrophysics Data System (ADS)

Chekhova, G. N.; Shubin, Yu. V.; Pinakov, D. V.; Alferova, N. I.

2008-07-01

Phase equilibria in the thiourea (host)-bromoform (guest) binary system were studied by physicochemical analysis methods over the temperature range 270 455 K. The stoichiometry and stability region were determined for the channel-type compound CHBr3 · 2.40(2)(NH2)2CS; the compound was observed for the first time. When heated, the clathrate incongruently decomposed at 424.0 ± 0.8 K to rhombic thiourea and the guest component. The solubility isotherm of the thiourea-bromoform-acetic acid system was studied to find that the compound was thermodynamically stable at 293 K over the range of guest component concentrations 100 35 wt %. A decrease in its content in an equilibrium mother liquor resulted in the appearance of X-ray diffraction reflections of the initial host α polymorph. Rhombohedral cell parameters were determined (space group R-3 c, a = 15.89(1) Å, c = 12.40(1) Å, V = 2711(6) Å3, d calcd = 2.000 g/cm3, and d expt = 1.98(2) g/cm3). The mode of packing of bromoform molecules was compared with the organization of the guest subsystem in inclusion compounds formed by the substances studied.

Carrier generation and electronic properties of a single-component pure organic metal

NASA Astrophysics Data System (ADS)

Kobayashi, Yuka; Terauchi, Takeshi; Sumi, Satoshi; Matsushita, Yoshitaka

2017-01-01

Metallic conduction generally requires high carrier concentration and wide bandwidth derived from strong orbital interaction between atoms or molecules. These requisites are especially important in organic compounds because a molecule is fundamentally an insulator; only multi-component salts with strong intermolecular interaction--namely, only charge transfer complexes and conducting polymers--have demonstrated intrinsic metallic behaviour. Herein we report a single-component electroactive molecule, zwitterionic tetrathiafulvalene(TTF)-extended dicarboxylate radical (TED), exhibiting metallic conduction even at low temperatures. TED exhibits d.c. conductivities of 530 S cm-1 at 300 K and 1,000 S cm-1 at 50 K with copper-like electronic properties. Spectroscopic and theoretical investigations of the carrier-generation mechanism and the electronic states of this single molecular species reveal a unique electronic structure with a spin-density gradient in the extended TTF moieties that becomes, in itself, a metallic state.

Sensor devices comprising a metal-organic framework material and methods of making and using the same

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

Wang, Alan X.; Chang, Chih-hung; Kim, Ki-Joong

Disclosed herein are embodiments of sensor devices comprising a sensing component able to determine the presence of, detect, and/or quantify detectable species in a variety of environments and applications. The sensing components disclosed herein can comprise MOF materials, plasmonic nanomaterials, or combinations thereof. In an exemplary embodiment, light guides can be coupled with the sensing components described herein to provide sensor devices capable of increased NIR detection sensitivity in determining the presence of detectable species, such as gases and volatile organic compounds. In another exemplary embodiment, optical properties of the plasmonic nanomaterials combined with MOF materials can be monitored directlymore » to detect analyte species through their impact on external conditions surrounding the particle or as a result of charge transfer to and from the plasmonic material as a result of interactions with the plasmonic material and/or the MOF material.« less

CLEANER SYNTHESIS OF ORGANIC COMPOUNDS USING NANO-STRUCTURED TIO2 PREPARED BY FLAME AEROSOL METHOD

EPA Science Inventory

The chemical industry is a significant component of the domestic economy, generating well over $250 billion in sales and a trade surplus exceeding $15 billion in each of the last 5 years. The industry is also a major source of industrial waste and is the dominant source of hazard...

Composition of the organic components in polyxometalate (POM) liquors from kraft pulp bleaching

Treesearch

Biljana Bujanovic; Kolby C. Hirth; Sally A. Ralph; Richard S. Reiner; Rajai H. Atalla

2007-01-01

Promising results from the selective oxidative delignification of kraft pulp with polyoxometalates (POMs) prompted interest in elucidating the lignin oxidation mechanism. The degradation of lignin model compounds and residual lignin in kraft pulps, upon treatment with POMs was studied and differences in the reaction mechanisms between guaiacyl (G-) and syringyl (S-)...

Preparation of polyurethane foams using fractionated products in liquefied wood

Treesearch

Junming Xu; Jianchun Jiang; Chung-Yun Hse; Todd F. Shupe

2014-01-01

Liquefaction of sawdust was studied using glycerol and methanol as mix solvents. A new bio-polyol product consisting of high purity multi-hydroxy compounds was obtained by precipitation of the hydrophobic organics from the liquefied product in an aqueous solution. As identified by GC-MS, the dominate components in bio-polyol were glycerol, glycerol derivatives, and...

The influence of organic-mineral complexes on micro-elements dynamic in ecological systems of vegetables cultivation

NASA Astrophysics Data System (ADS)

Bulgariu, D.; Buzgar, N.; Bulgariu, L.; Rusu, C.; Munteanu, N.

2009-04-01

In ecological systems of vegetable cultivation (hortic antrosols; soils from greenhouses), exists an ensemble of equilibriums between organic-mineral combinations, very sensitive even to relatively small variations of physical-chemical conditions in soils. As such, these can manifest a strong influence on organic matter, clay minerals and microelements from soil, which in turn impacts on the productivity of these soils and the quality of obtained products (vegetables, fruit). Although many studies consider these organic-mineral combinations are meta-stable combinations, our work has shown that the stability of organic-mineral combinations in hortic antrosols (especially for clay-humic, clay-ironhumic combinations and chelates) is higher. We believe that this is due to the higher flexibility of these combinations' structures with the variation of chemical-mineralogical composition and physical-chemical conditions in soil. This paper highlights the results of our research on the differentiation possibility of organic-mineral complexes, depending on their structure and composition (using Raman and FT-IR spectrometry) and the influences manifested by the organic-mineral complexes on the micro-elements dynamic from ecological systems of fresh vegetable cultivation. The non-destructive separation of organic-mineral compounds from soil samples was carried out through iso-dynamic magnetic separation and extraction in aqueous two-phase systems (PEG-based). The Raman and FT-IR spectrometry analyses on raw soil samples, extracts obtained from soil samples and separated mineral fractions have been supplemented by the results obtained through chemical, microscopic and thermal analyses and by UV-VIS absorption spectrometry. Ours experimental studies have been done on representative samples of hortic antrosol from Copou glasshouse (Iasi, Romania), and was studied five micro-elements: Zn, Ni, Cu, Mn, Cr and P. The total contents of the five microelements and their fractions differential bonded on mineral and organic components of hortic antrosols, have been determined by atomic absorption spectrometry after combined sequential extraction in solid phase extraction - aqueous biphasic (PEG based) systems. The specific mechanisms of the microelements interaction with organic components have been estimated on the basis of studies realized on fractions obtained after each extraction step by Raman and FTIR spectrometry. These data have been correlated with those obtained by chemical analysis and UV-VIS spectrometry. In conditions of hortic antrosol, from total contents of Zn, Ni, Cu, Mn and Cr, more than 65 % are binding on organic components. A specific phenomenon of hortic antrosols is the microelements complexation exclusively with the functional groups of organic macromolecules. This phenomenon has two important consequences: (i) the strong fixation of microelements (these can be extracted only in very extremely conditions, which implied the organic part destroying) and (ii) their presence determined major modifications in the structure, conformation and stability of organic macromolecules. Under these conditions, the type and structure of organic-mineral compounds represent determinant factors for the dynamic of micro-elements and organic compounds in ecological systems of vegetables cultivation. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07 an Project PNCDI 2-D5 no. 52141 / 08).

Development of a NIST standard reference material containing thirty volatile organic compounds at 5 nmol/mol in nitrogen.

PubMed

Rhoderick, George C; Yen, James H

2006-05-01

Primary gravimetric gas cylinder standards containing 30 volatile organic compounds (VOCs) in nitrogen were prepared using a procedure previously developed to prepare gas mixture cylinder standards of VOCs at the 5 nmol/mol level. This set of primary standards was intercompared to existing gas cylinder standards, containing as many as 19 of the 30 volatile organics present in these new primaries, using gas chromatography with a hydrogen flame ionization detector coupled with cryogenic preconcentration. The linear regression analysis showed excellent agreement among the standards for each compound. Similar mixtures containing many of these compounds in treated aluminum gas cylinders have been evaluated over time and have shown stability for as much as 10 years. The development of these 30-component primary standards led to the preparation and certification of a reissue of Standard Reference Material (SRM) 1804 at the nominal amount-of-substance fraction of 5 nmol/mol for each analyte. A lot of 20 cylinders containing the mixture was prepared at NIST following previously demonstrated protocols for preparation of the cylinders. Each cylinder was analyzed against one cylinder from the lot, designated as the "lot standard," for each of the 30 compounds. As a result of the uncertainty analysis, the data showed that rather than declaring the lot homogeneous with a much higher uncertainty, each cylinder could be individually certified. The expanded uncertainty limits ranged from 1.5 to 10% for 28 of the 30 analytes, with two of the analytes having uncertainties as high as 19% in those SRM cylinders certified. Due to stability issues and some high uncertainties for a few analytes in 2 of the samples, 18 of the 20 candidate SRM samples were certified. These volatile organic gas mixtures represent the most complex gas SRMs developed at NIST.

Evaluation of the separation characteristics of application-specific (volatile organic compounds) open-tubular columns for gas chromatography.

PubMed

Poole, Colin F; Qian, Jing; Kiridena, Waruna; Dekay, Colleen; Koziol, Wladyslaw W

2006-11-17

The solvation parameter model is used to characterize the separation characteristics of two application-specific open-tubular columns (Rtx-Volatiles and Rtx-VGC) and a general purpose column for the separation of volatile organic compounds (DB-WAXetr) at five equally spaced temperatures over the range 60-140 degrees C. System constant differences and retention factor correlation plots are then used to determine selectivity differences between the above columns and their closest neighbors in a large database of system constants and retention factors for forty-four open-tubular columns. The Rtx-Volatiles column is shown to have separation characteristics predicted for a poly(dimethyldiphenylsiloxane) stationary phase containing about 16% diphenylsiloxane monomer. The Rtx-VGC column has separation properties similar to the poly(cyanopropylphenyldimethylsiloxane) stationary phase containing 14% cyanopropylphenylsiloxane monomer DB-1701 for non-polar and dipolar/polarizable compounds but significantly different characteristics for the separation of hydrogen-bond acids. For all practical purposes the DB-WAXetr column is shown to be selectivity equivalent to poly(ethylene glycol) columns prepared using different chemistries for bonding and immobilizing the stationary phase. Principal component analysis and cluster analysis are then used to classify the system constants for the above columns and a sub-database of eleven open-tubular columns (DB-1, HP-5, DB-VRX, Rtx-20, DB-35, Rtx-50, Rtx-65, DB-1301, DB-1701, DB-200, and DB-624) commonly used for the separation of volatile organic compounds. A rationale basis for column selection based on differences in intermolecular interactions is presented as an aid to method development for the separation of volatile organic compounds.

The organic inventory of primitive meteorites

NASA Astrophysics Data System (ADS)

Martins, Zita

Carbonaceous meteorites are primitive samples that provide crucial information about the solar system genesis and evolution. This class of meteorites has also a rich organic inventory, which may have contributed the first prebiotic building blocks of life to the early Earth. We have studied the soluble organic inventory of several CR and CM meteorites, using high performance liquid chromatography with UV fluorescence detection (HPLC-FD), gas chromatography-mass spectrometry (GC-MS) and gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). Our target organic molecules include amino acids, nucleobases and polycyclic aromatic hydrocarbons (PAHs), among others. CR chondrites contain the highest amino acids concentration ever detected in a meteorite. The degree of aqueous alteration amongst this class of meteorites seems to be responsible for the amino acid distribution. Pioneering compound-specific carbon isotope measurements of nucleobases present in carbonaceous chondrites show that these compounds have a non-terrestrial origin. This suggests that components of the ge-netic code may have had a crucial role in life's origin. Investigating the abundances, distribution and isotopic composition of organic molecules in primitive meteorites significantly improves our knowledge of the chemistry of the early solar system, and the resources available for the first living organisms on Earth.

Concentration and fractionation of hydrophobic organic acid constituents from natural waters by liquid chromatography

USGS Publications Warehouse

Thurman, E.M.; Malcolm, R.L.

1979-01-01

A scheme is presented which used adsorption chromatography with pH gradient elution and size-exclusion chromatography to concentrate and separate hydrophobic organic acids from water. A review of chromatographic processes involved in the flow scheme is also presented. Organic analytes which appear in each aqueous fraction are quantified by dissolved organic carbon analysis. Hydrophobic organic acids in a water sample are concentrated on a porous acrylic resin. These acids usually constitute approximately 30-50 percent of the dissolved organic carbon in an unpolluted water sample and are eluted with an aqueous eluent (dilute base). The concentrate is then passed through a column of polyacryloylmorpholine gel, which separates the acids into high- and low-molecular-weight fractions. The high- and low-molecular-weight eluates are reconcentrated by adsorption chromatography, then are eluted with a pH gradient into strong acids (predominately carboxylic acids) and weak acids (predominately phenolic compounds). For standard compounds and samples of unpolluted waters, the scheme fractionates humic substances into strong and weak acid fractions that are separated from the low molecular weight acids. A new method utilizing conductivity is also presented to estimate the acidic components in the methanol fraction.

[Detection of organic compounds on Mars].

PubMed

Kobayashi, K

1997-03-01

McKay et al. detected polycyclic aromatic hydrocarbons (PAHs) in Martian meteorite ALH 84001 by two-step laser mass spectrometry. From the presence of PAHs, together with other results, they concluded that there were past life of Mars. On the other hands, no organisms nor organic compounds were detected in Martian regolith in Viking experiments in 1976. In order to obtain solid evidence for organisms or bioorganic compounds compounds on Mars, further analyses of Martian samples are required. There may be four classes of organic compounds on Mars, which are (i) organic compounds abiotically formed from primitive Mars atmosphere, (ii) Organic compounds delivered out of Mars, (iii) Organic compounds biotically formed by Mars organisms, and (iv) Organic compounds abiotically formed from the present Mars atmosphere. Possible organic compounds on Mars and analytical methods for them are discussed.

Monoacylglycerols are components of root waxes and can be produced in the aerial cuticle by ectopic expression of a suberin-associated acyltransferase.

PubMed

Li, Yonghua; Beisson, Fred; Ohlrogge, John; Pollard, Mike

2007-07-01

The interface between plants and the environment is provided for aerial organs by epicuticular waxes that have been extensively studied. By contrast, little is known about the nature, biosynthesis, and role of waxes at the root-rhizosphere interface. Waxes isolated by rapid immersion of Arabidopsis (Arabidopsis thaliana) roots in organic solvents were rich in saturated C18-C22 alkyl esters of p-hydroxycinnamic acids, but also contained significant amounts of both alpha- and beta-isomers of monoacylglycerols with C22 and C24 saturated acyl groups and the corresponding free fatty acids. Production of these compounds in root waxes was positively correlated to the expression of sn-glycerol-3-P acyltransferase5 (GPAT5), a gene encoding an acyltransferase previously shown to be involved in aliphatic suberin synthesis. This suggests a direct metabolic relationship between suberin and some root waxes. Furthermore, when ectopically expressed in Arabidopsis, GPAT5 produced very-long-chain saturated monoacylglycerols and free fatty acids as novel components of cuticular waxes. The crystal morphology of stem waxes was altered and the load of total stem wax compounds was doubled, although the major components typical of the waxes found on wild-type plants decreased. These results strongly suggest that GPAT5 functions in vivo as an acyltransferase to a glycerol-containing acceptor and has access to the same pool of acyl intermediates and/or may be targeted to the same membrane domain as that of wax synthesis in aerial organs.

Urey: Mars Organic and Oxidant Detector

NASA Technical Reports Server (NTRS)

2007-01-01

[figure removed for brevity, see original site] Annotated Version

Some key components of a NASA-funded instrument being developed for the payload of the European Space Agency's ExoMars mission stand out in this illustration of the instrument.

The instrument is the Urey: Mars Organic and Oxidant Detector. It can check for the faintest traces of life's molecular building blocks. If those are present, it can assess whether they were produced by anything alive. It can also evaluate harsh environmental conditions that could be erasing those molecular clues.

ExoMars is planned as a rover to be launched in 2013 and search on Mars for signs of life.

Samples of Martian soil collected by a drill on the rover will be delivered to the Urey instrument. The instrument component called the sub-critical water extractor adds water and heats the sample, getting different types of organic compounds to dissolve into the water at different temperatures. The Mars organic detector uses a fluorescent reagent and laser to detect organic chemicals. The micro-capillary electrophoresis component separates different types of organic chemicals from each others for identifying which ones are present in the sample. The Mars oxidant instrument, part of which is on a separately mounted deck unit not pictured, assesses how readily organic material would be broken down by the radiation, atmosphere and soil chemistry of the site.

VOC source identification from personal and residential indoor, outdoor and workplace microenvironment samples in EXPOLIS-Helsinki, Finland

NASA Astrophysics Data System (ADS)

Edwards, Rufus D.; Jurvelin, J.; Koistinen, K.; Saarela, K.; Jantunen, M.

Principal component analyses (varimax rotation) were used to identify common sources of 30 target volatile organic compounds (VOCs) in residential outdoor, residential indoor and workplace microenvironment and personal 48-h exposure samples, as a component of the EXPOLIS-Helsinki study. Variability in VOC concentrations in residential outdoor microenvironments was dominated by compounds associated with long-range transport of pollutants, followed by traffic emissions, emissions from trees and product emissions. Variability in VOC concentrations in environmental tobacco smoke (ETS) free residential indoor environments was dominated by compounds associated with indoor cleaning products, followed by compounds associated with traffic emissions, long-range transport of pollutants and product emissions. Median indoor/outdoor ratios for compounds typically associated with traffic emissions and long-range transport of pollutants exceeded 1, in some cases quite considerably, indicating substantial indoor source contributions. Changes in the median indoor/outdoor ratios during different seasons reflected different seasonal ventilation patterns as increased ventilation led to dilution of those VOC compounds in the indoor environment that had indoor sources. Variability in workplace VOC concentrations was dominated by compounds associated with traffic emissions followed by product emissions, long-range transport and air fresheners. Variability in VOC concentrations in ETS free personal exposure samples was dominated by compounds associated with traffic emissions, followed by long-range transport, cleaning products and product emissions. VOC sources in personal exposure samples reflected the times spent in different microenvironments, and personal exposure samples were not adequately represented by any one microenvironment, demonstrating the need for personal exposure sampling.

Analysis of antioxidative phenolic compounds in artichoke (Cynara scolymus L.).

PubMed

Wang, Mingfu; Simon, James E; Aviles, Irma Fabiola; He, Kan; Zheng, Qun-Yi; Tadmor, Yaakov

2003-01-29

Artichoke leaf is an herbal medicine known for a long time. A systematic antioxidant activity-directed fractionation procedure was used to purify antioxidative components from the aqueous methanol extractions of artichoke heads and leaves in this study. Seven active polyphenolic compounds were purified from artichoke, and structural elucidation of each was achieved using MS and NMR. Two of these compounds, apigenin-7-rutinoside and narirutin, were found to be unique to artichoke heads, this represents the first report of these compounds in the edible portion of this plant. The contents of these antioxidants and total phenols in dried artichoke samples from leaves and immature and mature heads of three varieties, Imperial Star, Green Globe, and Violet, were then analyzed and compared by colorimetric and validated HPLC methods. Significant differences by variety and plant organ were observed.

Trace detection of organic compounds in complex sample matrixes by single photon ionization ion trap mass spectrometry: real-time detection of security-relevant compounds and online analysis of the coffee-roasting process.

PubMed

Schramm, Elisabeth; Kürten, Andreas; Hölzer, Jasper; Mitschke, Stefan; Mühlberger, Fabian; Sklorz, Martin; Wieser, Jochen; Ulrich, Andreas; Pütz, Michael; Schulte-Ladbeck, Rasmus; Schultze, Rainer; Curtius, Joachim; Borrmann, Stephan; Zimmermann, Ralf

2009-06-01

An in-house-built ion trap mass spectrometer combined with a soft ionization source has been set up and tested. As ionization source, an electron beam pumped vacuum UV (VUV) excimer lamp (EBEL) was used for single-photon ionization. It was shown that soft ionization allows the reduction of fragmentation of the target analytes and the suppression of most matrix components. Therefore, the combination of photon ionization with the tandem mass spectrometry (MS/MS) capability of an ion trap yields a powerful tool for molecular ion peak detection and identification of organic trace compounds in complex matrixes. This setup was successfully tested for two different applications. The first one is the detection of security-relevant substances like explosives, narcotics, and chemical warfare agents. One test substance from each of these groups was chosen and detected successfully with single photon ionization ion trap mass spectrometry (SPI-ITMS) MS/MS measurements. Additionally, first tests were performed, demonstrating that this method is not influenced by matrix compounds. The second field of application is the detection of process gases. Here, exhaust gas from coffee roasting was analyzed in real time, and some of its compounds were identified using MS/MS studies.

Sol-gel-based SPME fiber as a reliable sampling technique for studying biogenic volatile organic compounds released from Clostridium tetani.

PubMed

Ghader, Masoud; Shokoufi, Nader; Es-Haghi, Ali; Kargosha, Kazem

2017-11-01

A novel and efficient headspace solid-phase microextraction (HS-SPME) method, followed by gas chromatography mass spectrometry (GC-MS), was developed to study volatile organic compounds (VOCs) emerging from microorganisms. Two homemade SPME fibers, a semi-polar poly (dimethylsiloxane) (PDMS) fiber, and a polar polyethylene glycol (PEG) fiber, along with two commercial fibers (PDMS and PDMS/DVB) were used to collect VOCs emerging from Clostridium tetani which was cultured in different media. The adsorbed VOCs were desorbed and identified, in vitro, using GC-MS. The adsorption efficiency was improved by optimizing the time duration of adsorption and desorption. About 50 components were identified by the proposed method. The main detected compounds appeared to be sulfur containing compounds such as butanethioic acid S-methyl ester, dimethyl trisulfide, and dimethyl tetrasulfide. These volatile sulfur containing compounds are derived from amino acids containing the sulfur element, which probably coexist in the mentioned bacterium or are added to the culture media. The developed HS-SPME-GC-MS method allowed the determination of the chemical fingerprint of Clostridium tetani volatile constituents, and thus provides a new, simple, and reliable tool for studying the growth of microorganisms. Graphical abstract Investigation of biogenic VOCs released from Clostridium tetani using SPME-GC-MS.

Crystal and molecular structure of eight organic acid-base adducts from 2-methylquinoline and different acids

NASA Astrophysics Data System (ADS)

Zhang, Jing; Jin, Shouwen; Tao, Lin; Liu, Bin; Wang, Daqi

2014-08-01

Eight supramolecular complexes with 2-methylquinoline and acidic components as 4-aminobenzoic acid, 2-aminobenzoic acid, salicylic acid, 5-chlorosalicylic acid, 3,5-dinitrosalicylic acid, malic acid, sebacic acid, and 1,5-naphthalenedisulfonic acid were synthesized and characterized by X-ray crystallography, IR, mp, and elemental analysis. All of the complexes are organic salts except compound 2. All supramolecular architectures of 1-8 involve extensive classical hydrogen bonds as well as other noncovalent interactions. The results presented herein indicate that the strength and directionality of the classical hydrogen bonds (ionic or neutral) between acidic components and 2-methylquinoline are sufficient to bring about the formation of binary organic acid-base adducts. The role of weak and strong noncovalent interactions in the crystal packing is ascertained. These weak interactions combined, the complexes 1-8 displayed 2D-3D framework structure.

Global distribution and surface activity of macromolecules in offline simulations of marine organic chemistry

DOE PAGES

Ogunro, Oluwaseun O.; Burrows, Susannah M.; Elliott, Scott; ...

2015-10-13

Here, organic macromolecules constitute high percentage components of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer organic macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean biogeochemistry model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed formore » labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of protein, polysaccharide and refractory heteropolycondensate. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally quite reasonable. Global distributions are further estimated for both fractional coverage of bubble films at the air-water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant distributions. Results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change.« less

Characterisation of landfill leachate by EEM-PARAFAC-SOM during physical-chemical treatment by coagulation-flocculation, activated carbon adsorption and ion exchange.

PubMed

Oloibiri, Violet; De Coninck, Sam; Chys, Michael; Demeestere, Kristof; Van Hulle, Stijn W H

2017-11-01

The combination of fluorescence excitation-emission matrices (EEM), parallel factor analysis (PARAFAC) and self-organizing maps (SOM) is shown to be a powerful tool in the follow up of dissolved organic matter (DOM) removal from landfill leachate by physical-chemical treatment consisting of coagulation, granular activated carbon (GAC) and ion exchange. Using PARAFAC, three DOM components were identified: C1 representing humic/fulvic-like compounds; C2 representing tryptophan-like compounds; and C3 representing humic-like compounds. Coagulation with ferric chloride (FeCl 3 ) at a dose of 7 g/L reduced the maximum fluorescence of C1, C2 and C3 by 52%, 17% and 15% respectively, while polyaluminium chloride (PACl) reduced C1 only by 7% at the same dose. DOM removal during GAC and ion exchange treatment of raw and coagulated leachate exhibited different profiles. At less than 2 bed volumes (BV) of treatment, the humic components C1 and C3 were rapidly removed, whereas at BV ≥ 2 the tryptophan-like component C2 was preferentially removed. Overall, leachate treated with coagulation +10.6 BV GAC +10.6 BV ion exchange showed the highest removal of C1 (39% - FeCl 3 , 8% - PACl), C2 (74% - FeCl 3 , 68% - PACl) and no C3 removal; whereas only 52% C2 and no C1 and C3 removal was observed in raw leachate treated with 10.6 BV GAC + 10.6 BV ion exchange only. Analysis of PARAFAC-derived components with SOM revealed that coagulation, GAC and ion exchange can treat leachate at least 50% longer than only GAC and ion exchange before the fluorescence composition of leachate remains unchanged. Copyright © 2017 Elsevier Ltd. All rights reserved.

Molecular composition of organic aerosol over an agricultural site in North China Plain: Contribution of biogenic sources to PM2.5

NASA Astrophysics Data System (ADS)

Li, Xingru; Liu, Yusi; Li, Dong; Wang, Guoan; Bai, Yu; Diao, Heling; Shen, Rongrong; Hu, Bo; Xin, Jinyuan; Liu, Zirui; Wang, Yuesi; Guo, Xueqing; Wang, Lili

2017-09-01

Sugars and biogenic secondary organic aerosols (BSOAs) are substantial components of particulate organic matter, which affects regional and global air quality and climate. Fine particulate matter (PM2.5) samples were collected from 20 June to 30 July 2015 on a diurnal/nocturnal cycle in Yucheng, China in the North China Plain. The PM2.5 samples were analyzed for sugars and SOA tracers derived from biogenic volatile organic compounds (BVOCs) and other compounds, such as water soluble ions, element carbon (EC), organic carbon (OC) and water soluble organic carbon (WSOC). The quantified organic components accounted for 4.7% and 0.4% of the OC and PM2.5, respectively. SOA tracer concentrations were weakly higher during the day (101.6 ± 61.7 ng m-3) than at night (90.2 ± 41.5 ng m-3)(t = 0.610, P > 0.05), whereas sugar showed higher concentrations at night (227.0 ± 196.9 ng m-3) than during the day (177.9 ± 145.4 ng m-3)(t = -1.329, P > 0.05). Anhydro sugar (mannosan, galactosan, and levoglucosan) were the main components of the measured sugars and accounted for 58.5% and 75.6% of the daytime and nighttime measurements. The levoglucosan/mannosan ratios were 20.2 ± 12.9 and 17.6 ± 9.1 for the daytime and nighttime samples, respectively, indicating that crop residues, herbaceous plants and hardwood were the dominant types of biomass burned in the Yucheng region. Isoprene SOA tracers exhibited the highest levels among the measured SOA tracers, followed by α-pinene SOA tracers. The concentration of BSOC estimated using the tracer method was 3.9-1817.5 ng C m-3 and accounted for 0.1-26.0% of the OC. A clear negative correlation (r = 0.53) between isoprene-derived SOA and in-situ pH demonstrated that acid-catalyzed heterogeneous reactions can significantly enhance SOA mass. In addition, isoprene-derived SOA increased with the relative humidity (RH) when the RH was lower than 50%, whereas it decreased when the RH was higher than 50%.

Ultrasonic degradation of acetaminophen in water: effect of sonochemical parameters and water matrix.

PubMed

Villaroel, Erica; Silva-Agredo, Javier; Petrier, Christian; Taborda, Gonzalo; Torres-Palma, Ricardo A

2014-09-01

This paper deals about the sonochemical water treatment of acetaminophen (ACP, N-acetyl-p-aminophenol or paracetamol), one of the most popular pharmaceutical compounds found in natural and drinking waters. Effect of ultrasonic power (20-60 W), initial ACP concentration (33-1323 μmol L(-1)) and pH (3-12) were evaluated. High ultrasonic powers and, low and natural acidic pH values favored the efficiency of the treatment. Effect of initial substrate concentration showed that the Langmuir-type kinetic model fit well the ACP sonochemical degradation. The influence of organic compounds in the water matrix, at concentrations 10-fold higher than ACP, was also evaluated. The results indicated that only organic compounds having a higher value of the Henry's law constant than the substrate decrease the efficiency of the treatment. On the other hand, ACP degradation in mineral natural water showed to be strongly dependent of the initial substrate concentration. A positive matrix effect was observed at low ACP concentrations (1.65 μmol L(-1)), which was attributed to the presence of bicarbonate ion in solution. However, at relative high ACP concentrations a detrimental effect of matrix components was noticed. Finally, the results indicated that ultrasonic action is able to transform ACP in aliphatic organic compounds that could be subsequently eliminated in a biological system. Copyright © 2014 Elsevier B.V. All rights reserved.

Alkylation of organic aromatic compounds

DOEpatents

Smith, L.A. Jr.

1989-07-18

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

Alkylation of organic aromatic compounds

DOEpatents

Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

1994-01-01

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

Alkylation of organic aromatic compounds

DOEpatents

Smith, Jr., Lawrence A.

1989-01-01

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

Alkylation of organic aromatic compounds

DOEpatents

Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

1994-06-14

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

Quadratic integrand double-hybrid made spin-component-scaled

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

Brémond, Éric, E-mail: eric.bremond@iit.it; Savarese, Marika; Sancho-García, Juan C.

2016-03-28

We propose two analytical expressions aiming to rationalize the spin-component-scaled (SCS) and spin-opposite-scaled (SOS) schemes for double-hybrid exchange-correlation density-functionals. Their performances are extensively tested within the framework of the nonempirical quadratic integrand double-hybrid (QIDH) model on energetic properties included into the very large GMTKN30 benchmark database, and on structural properties of semirigid medium-sized organic compounds. The SOS variant is revealed as a less computationally demanding alternative to reach the accuracy of the original QIDH model without losing any theoretical background.

General Analytical Procedure for Determination of Acidity Parameters of Weak Acids and Bases

PubMed Central

Pilarski, Bogusław; Kaliszan, Roman; Wyrzykowski, Dariusz; Młodzianowski, Janusz; Balińska, Agata

2015-01-01

The paper presents a new convenient, inexpensive, and reagent-saving general methodology for the determination of pK a values for components of the mixture of diverse chemical classes weak organic acids and bases in water solution, without the need to separate individual analytes. The data obtained from simple pH-metric microtitrations are numerically processed into reliable pK a values for each component of the mixture. Excellent agreement has been obtained between the determined pK a values and the reference literature data for compounds studied. PMID:25692072

General analytical procedure for determination of acidity parameters of weak acids and bases.

PubMed

Pilarski, Bogusław; Kaliszan, Roman; Wyrzykowski, Dariusz; Młodzianowski, Janusz; Balińska, Agata

2015-01-01

The paper presents a new convenient, inexpensive, and reagent-saving general methodology for the determination of pK a values for components of the mixture of diverse chemical classes weak organic acids and bases in water solution, without the need to separate individual analytes. The data obtained from simple pH-metric microtitrations are numerically processed into reliable pK a values for each component of the mixture. Excellent agreement has been obtained between the determined pK a values and the reference literature data for compounds studied.

Comparison of Methods for Predicting the Compositional Dependence of the Density and Refractive Index of Organic-Aqueous Aerosols.

PubMed

Cai, Chen; Miles, Rachael E H; Cotterell, Michael I; Marsh, Aleksandra; Rovelli, Grazia; Rickards, Andrew M J; Zhang, Yun-Hong; Reid, Jonathan P

2016-08-25

Representing the physicochemical properties of aerosol particles of complex composition is of crucial importance for understanding and predicting aerosol thermodynamic, kinetic, and optical properties and processes and for interpreting and comparing analysis methods. Here, we consider the representations of the density and refractive index of aqueous-organic aerosol with a particular focus on the dependence of these properties on relative humidity and water content, including an examination of the properties of solution aerosol droplets existing at supersaturated solute concentrations. Using bulk phase measurements of density and refractive index for typical organic aerosol components, we provide robust approaches for the estimation of these properties for aerosol at any intermediate composition between pure water and pure solute. Approximately 70 compounds are considered, including mono-, di- and tricarboxylic acids, alcohols, diols, nitriles, sulfoxides, amides, ethers, sugars, amino acids, aminium sulfates, and polyols. We conclude that the molar refraction mixing rule should be used to predict the refractive index of the solution using a density treatment that assumes ideal mixing or, preferably, a polynomial dependence on the square root of the mass fraction of solute, depending on the solubility limit of the organic component. Although the uncertainties in the density and refractive index predictions depend on the range of subsaturated compositional data available for each compound, typical errors for estimating the solution density and refractive index are less than ±0.1% and ±0.05%, respectively. Owing to the direct connection between molar refraction and the molecular polarizability, along with the availability of group contribution models for predicting molecular polarizability for organic species, our rigorous testing of the molar refraction mixing rule provides a route to predicting refractive indices for aqueous solutions containing organic molecules of arbitrary structure.

Inhibition of DNA polymerase λ and associated inflammatory activities of extracts from steamed germinated soybeans.

PubMed

Mizushina, Yoshiyuki; Kuriyama, Isoko; Yoshida, Hiromi

2014-04-01

During the screening of selective DNA polymerase (pol) inhibitors from more than 50 plant food materials, we found that the extract from steamed germinated soybeans (Glycine max L.) inhibited human pol λ activity. Among the three processed soybean samples tested (boiled soybeans, steamed soybeans, and steamed germinated soybeans), both the hot water extract and organic solvent extract from the steamed germinated soybeans had the strongest pol λ inhibition. We previously isolated two glucosyl compounds, a cerebroside (glucosyl ceramide, AS-1-4, compound ) and a steroidal glycoside (eleutheroside A, compound ), from dried soybean, and these compounds were prevalent in the extracts of the steamed germinated soybeans as pol inhibitors. The hot water and organic solvent extracts of the steamed germinated soybeans and compounds and selectively inhibited the activity of eukaryotic pol λ in vitro but did not influence the activities of other eukaryotic pols, including those from the A-family (pol γ), B-family (pols α, δ, and ε), and Y-family (pols η, ι, and κ), and also showed no effect on the activity of pol β, which is of the same family (X) as pol λ. The tendency for in vitro pol λ inhibition by these extracts and compounds showed a positive correlation with the in vivo suppression of TPA (12-O-tetradecanoylphorbol-13-acetate)-induced inflammation in mouse ear. These results suggest that steamed germinated soybeans, especially the glucosyl compound components, may be useful for their anti-inflammatory properties.

An endophytic Coniochaeta velutina producing broad spectrum antimycotics.

PubMed

Xie, Jie; Strobel, Gary A; Feng, Tao; Ren, Huishuang; Mends, Morgan T; Zhou, Zeyang; Geary, Brad

2015-06-01

An endophyte (PC27-5) was isolated from stem tissue of Western hemlock (Tsuga heterophylla) in a Pacific Northwest temperate rainforest. Phylogenetic analyses, based on ITS-5.8S rDNA and 18S rDNA sequence data, combined with cultural and morphological analysis showed that endophyte PC27-5 exhibited all characteristics of a fungus identical to Coniochaeta velutina. Furthermore, wide spectrum antimycotics were produced by this endophyte that were active against such plant pathogens as Sclerotinia sclerotiorum, Pythium ultimum, and Verticillium dahliae and lethal to Phythophthora cinnamomi, Pythium ultimum, and Phytophthora palmivora in plate tests. The bioactive components were purified through organic solvent extraction, followed by silica column chromatography, and finally preparative HPLC. The minimum inhibitory concentration of the active fraction to Pythium ultimum, which was gained from preparative HPLC, was 11 μg/ml. UPLC-HRMS analysis showed there were two similar components in the antimycotic fraction. Their molecular formulae were established as C30H22O11 (compound I) and C30H22O10 (compound II) respectively, and preliminary spectral results indicate that they are anthroquinone glycosides. Other non-biologically active compounds were identified in culture fluids of this fungus by spectral means as emodin and chrysophanol--anthroquinone derivatives. This is the first report that Coniochaeta velutina as an endophyte produces bioactive antifungal components.

Antibacterial Effect of Silver Diamine Fluoride on Cariogenic Organisms.

PubMed

Lou, Yali; Darvell, Brain W; Botelho, Michael G

2018-05-01

To screen the possible antimicrobial activity of a range of clinically used, silver-based compounds on cariogenic organisms: silver diamine fluoride (SDF), silver fluoride, and silver nitrate. Preliminary screening disk-diffusion susceptibility tests were conducted on Mueller-Hinton agar plates inoculated with Streptococcus mutans, Lactobacillus acidophilus, and Actinomyces naeslundii, organisms known to be cariogenic. In order to identify which component of the silver compounds was responsible for any antibacterial (AB) effect, and to provide controls, the following were also investigated at high and low concentrations: sodium fluoride, ammonium fluoride, ammonium chloride, sodium fluoride, sodium chloride, and sodium nitrate, as well as deionized water as control. A volume of 10 pL of a test solution was dispensed onto a paper disk resting on the inoculated agar surface, and the plate incubated anaerobically at 37°C for 48 hours. The zones of inhibition were then measured. Silver diamine fluoride, silver fluoride, silver nitrate, and ammonium fluoride had significant AB effect (p < 0.05) on all three test organisms, although ammonium fluoride had no effect at low concentration; the remaining other compounds had no effect. Silver ions appear to be the principal AB agent at both high and low concentration; fluoride ions only have an AB effect at high concentration, while ammonium, nitrate, chloride and sodium ions have none. The anticaries effect of topical silver solutions appears restricted to that of the silver ions. Silver compounds, such as SDF, silver fluoride, and silver nitrate have AB effect against cariogenic organisms and these may have clinical impact in arresting or preventing dental decay. Sodium fluoride did not have AB effect under the conditions tested.

Atmospheric PM and volatile organic compounds released from Mediterranean shrubland wildfires

NASA Astrophysics Data System (ADS)

Garcia-Hurtado, Elisa; Pey, Jorge; Borrás, Esther; Sánchez, Pilar; Vera, Teresa; Carratalá, Adoración; Alastuey, Andrés; Querol, Xavier; Vallejo, V. Ramon

2014-06-01

Wildfires produce a significant release of gases and particles affecting climate and air quality. In the Mediterranean region, shrublands significantly contribute to burned areas and may show specific emission profiles. Our objective was to depict and quantify the primary-derived aerosols and precursors of secondary particulate species released during shrubland experimental fires, in which fire-line intensity values were equivalent to those of moderate shrubland wildfires, by using a number of different methodologies for the characterization of organic and inorganic compounds in both gas-phase and particulate-phase. Emissions of PM mass, particle number concentrations and organic and inorganic PMx components during flaming and smouldering phases were characterized in a field shrubland fire experiment. Our results revealed a clear prevalence of K+ and SO42- as inorganic ions released during the flaming-smouldering processes, accounting for 68-80% of the inorganic soluble fraction. During the residual-smouldering phases, in addition to K+ and SO42-, Ca2+ was found in significant amounts probably due the predominance of re-suspension processes (ashes and soil dust) over other emission sources during this stage. Concerning organic markers, the chromatograms were dominated by phenols, n-alkanals and n-alkanones, as well as by alcohol biomarkers in all the PMx fractions investigated. Levoglucosan was the most abundant degradation compound with maximum emission factors between 182 and 261 mg kg-1 in PM2.5 and PM10 respectively. However, levoglucosan was also observed in significant amounts in the gas-phase. The most representative organic volatile constituents in the smoke samples were alcohols, carbonyls, acids, monocyclic and bicyclic arenes, isoprenoids and alkanes compounds. The emission factors obtained in this study may contribute to the validation and improvement of national and international emission inventories of this intricate and diffuse emission source.

Partial Resistance of Carrot to Alternaria dauci Correlates with In Vitro Cultured Carrot Cell Resistance to Fungal Exudates

PubMed Central

Voisine, Linda; Gatto, Julia; Hélesbeux, Jean-Jacques; Séraphin, Denis; Peña-Rodriguez, Luis M.; Richomme, Pascal; Boedo, Cora; Yovanopoulos, Claire; Gyomlai, Melvina; Briard, Mathilde; Simoneau, Philippe; Poupard, Pascal; Berruyer, Romain

2014-01-01

Although different mechanisms have been proposed in the recent years, plant pathogen partial resistance is still poorly understood. Components of the chemical warfare, including the production of plant defense compounds and plant resistance to pathogen-produced toxins, are likely to play a role. Toxins are indeed recognized as important determinants of pathogenicity in necrotrophic fungi. Partial resistance based on quantitative resistance loci and linked to a pathogen-produced toxin has never been fully described. We tested this hypothesis using the Alternaria dauci – carrot pathosystem. Alternaria dauci, causing carrot leaf blight, is a necrotrophic fungus known to produce zinniol, a compound described as a non-host selective toxin. Embryogenic cellular cultures from carrot genotypes varying in resistance against A. dauci were confronted with zinniol at different concentrations or to fungal exudates (raw, organic or aqueous extracts). The plant response was analyzed through the measurement of cytoplasmic esterase activity, as a marker of cell viability, and the differentiation of somatic embryos in cellular cultures. A differential response to toxicity was demonstrated between susceptible and partially resistant genotypes, with a good correlation noted between the resistance to the fungus at the whole plant level and resistance at the cellular level to fungal exudates from raw and organic extracts. No toxic reaction of embryogenic cultures was observed after treatment with the aqueous extract or zinniol used at physiological concentration. Moreover, we did not detect zinniol in toxic fungal extracts by UHPLC analysis. These results suggest that strong phytotoxic compounds are present in the organic extract and remain to be characterized. Our results clearly show that carrot tolerance to A. dauci toxins is one component of its partial resistance. PMID:24983469

Liquid chromatography coupled to on-line post column derivatization for the determination of organic compounds: a review on instrumentation and chemistries.

PubMed

Zacharis, Constantinos K; Tzanavaras, Paraskevas D

2013-10-10

Analytical derivatization either in pre or post column modes is one of the most widely used sample pretreatment techniques coupled to liquid chromatography. In the present review article we selected to discuss the post column derivatization mode for the analysis of organic compounds. The first part of the review focuses to the instrumentation of post-column setups including not only fundamental components such as pumps and reactors but also less common parts such as static mixers and back-pressure regulators; the second part of the article discusses the most popular "chemistries" that are involved in post column applications, including reagent-less approaches and new sensing platforms such as the popular gold nanoparticles. Some representative recent applications are also presented as tables. Copyright © 2013 Elsevier B.V. All rights reserved.

A litmus-type colorimetric and fluorometric volatile organic compound sensor based on inkjet-printed polydiacetylenes on paper substrates.

PubMed

Yoon, Bora; Park, In Sung; Shin, Hyora; Park, Hye Jin; Lee, Chan Woo; Kim, Jong-Man

2013-05-14

Inkjet-printed paper-based volatile organic compound (VOC) sensor strips imaged with polydiacetylenes (PDAs) are developed. A microemulsion ink containing bisurethane-substituted diacetylene (DA) monomers, 4BCMU, was inkjet printed onto paper using a conventional inkjet office printer. UV irradiation of the printed image allowed fabrication of blue-colored poly-4BCMU on the paper and the polymer was found to display colorimetric responses to VOCs. Interestingly, a blue-to-yellow color change was observed when the strip was exposed to chloroform vapor, which was accompanied by the generation of green fluorescence. The principal component analysis plot of the color and fluorescence images of the VOC-exposed polymers allowed a more precise discrimination of VOC vapors. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioactive formulations prepared from fruiting bodies and submerged culture mycelia of the Brazilian edible mushroom Pleurotus ostreatoroseus Singer.

PubMed

Corrêa, Rúbia Carvalho Gomes; de Souza, Aloisio Henrique Pereira; Calhelha, Ricardo C; Barros, Lillian; Glamoclija, Jasmina; Sokovic, Marina; Peralta, Rosane Marina; Bracht, Adelar; Ferreira, Isabel C F R

2015-07-01

Pleurotus ostreatoroseus is a Brazilian edible mushroom whose chemical characterization and bioactivity still remain underexplored. In this study, the hydrophilic and lipophilic compounds as well as the antioxidant, anti-inflammatory and antimicrobial activities of formulations (ethanol extracts) prepared with its fruiting bodies and submerged culture mycelia were compared. The bioactive formulations contain at least five free sugars, four organic acids, four phenolic compounds and two tocopherols. The fruiting body-based formulation revealed higher reducing power, DPPH scavenging activity, β-carotene bleaching inhibition and lipid peroxidation inhibition in brain homogenates than the mycelium-based preparation, as well as higher anti-inflammatory and antimicrobial activities. The absence of hepatotoxicity was confirmed in porcine liver primary cells. These functional responses can be related to the levels of bioactive components including phenolic acids, organic acids and tocopherols.

Oxalic Acid from Lentinula edodes Culture Filtrate: Antimicrobial Activity on Phytopathogenic Bacteria and Qualitative and Quantitative Analyses

PubMed Central

Kwak, A-Min; Lee, In-Kyoung; Lee, Sang-Yeop

2016-01-01

The culture filtrate of Lentinula edodes shows potent antimicrobial activity against the plant pathogenic bacteria Ralstonia solanacearum. Bioassay-guided fractionation was conducted using Diaion HP-20 column chromatography, and the insoluble active compound was not adsorbed on the resin. Further fractionation by high-performance liquid chromatography (HPLC) suggested that the active compounds were organic acids. Nine organic acids were detected in the culture filtrate of L. edodes; oxalic acid was the major component and exhibited antibacterial activity against nine different phytopathogenic bacteria. Quantitative analysis by HPLC revealed that the content of oxalic acid was higher in the water extract from spent mushroom substrate than in liquid culture. This suggests that the water extract of spent L. edodes substrate is an eco-friendly control agent for plant diseases. PMID:28154495

Dispersive liquid-liquid microextraction and gas chromatography accurate mass spectrometry for extraction and non-targeted profiling of volatile and semi-volatile compounds in grape marc distillates.

PubMed

Fontana, Ariel; Rodríguez, Isaac; Cela, Rafael

2018-04-20

The suitability of dispersive liquid-liquid microextraction (DLLME) and gas chromatography accurate mass spectrometry (GC-MS), based on a time-of-flight (TOF) MS analyzer and using electron ionization (EI), for the characterization of volatile and semi-volatile profiles of grape marc distillates (grappa) are evaluated. DLLME conditions are optimized with a selection of compounds, from different chemical families, present in the distillate spirit. Under final working conditions, 2.5 mL of sample and 0.5 mL of organic solvents are consumed in the sample preparation process. The absolute extraction efficiencies ranged from 30 to 100%, depending on the compound. For the same sample volume, DLLME provided higher responses than solid-phase microextraction (SPME) for most of the model compounds. The GC-EI-TOF-MS records of grappa samples were processed using a data mining non-targeted search algorithm. In this way, chromatographic peaks and accurate EI-MS spectra of sample components were linked. The identities of more than 140 of these components are proposed from comparison of their accurate spectra with those in a low resolution EI-MS database, accurate masses of most intense fragment ions of known structure, and available chromatographic retention index. The use of chromatographic and spectral data, associated to the set of components mined from different grappa samples, for multivariate analysis purposes is also illustrated in the study. Copyright © 2018 Elsevier B.V. All rights reserved.

Toxicity of benzotriazole and benzotriazole derivatives to three aquatic species.

PubMed

Pillard, D A; Cornell, J S; Dufresne, D L; Hernandez, M T

2001-02-01

Benzotriazole and its derivatives comprise an important class of corrosion inhibitors, typically used as trace additives in industrial chemical mixtures such as coolants, deicers, surface coatings, cutting fluids, and hydraulic fluids. Recent studies have shown that benzotriazole derivatives are a major component of aircraft deicing fluids (ADFs) responsible for toxicity to bacteria (Microtox). Our current research compared the toxicity of benzotriazole (BT), two methylbenzotriazole (MeBT) isomers, and butylbenzotriazole (BBT). Acute toxicity assays were used to model the response of three common test organisms: Microtox bacteria (Vibrio fischeri), fathead minnow (Pimephales promelas) and water flea (Ceriodaphnia dubia). The response of all the three organisms varied over two orders of magnitude among all compounds. Vibrio fischeri was more sensitive than either C. dubia or P. promelas to all the test materials, while C. dubia was less sensitive than P. promelas. The response of test organisms to unmethylated benzotriazole and 4-methylbenzotriazole was similar, whereas 5-methylbenzotriazole was more toxic than either of these two compounds. BBT was the most toxic benzotriazole derivative tested, inducing acute toxicity at a concentration of < or = 3.3 mg/l to all organisms.

Microbial Degradation of Petroleum Hydrocarbon Contaminants: An Overview

PubMed Central

Das, Nilanjana; Chandran, Preethy

2011-01-01

One of the major environmental problems today is hydrocarbon contamination resulting from the activities related to the petrochemical industry. Accidental releases of petroleum products are of particular concern in the environment. Hydrocarbon components have been known to belong to the family of carcinogens and neurotoxic organic pollutants. Currently accepted disposal methods of incineration or burial insecure landfills can become prohibitively expensive when amounts of contaminants are large. Mechanical and chemical methods generally used to remove hydrocarbons from contaminated sites have limited effectiveness and can be expensive. Bioremediation is the promising technology for the treatment of these contaminated sites since it is cost-effective and will lead to complete mineralization. Bioremediation functions basically on biodegradation, which may refer to complete mineralization of organic contaminants into carbon dioxide, water, inorganic compounds, and cell protein or transformation of complex organic contaminants to other simpler organic compounds by biological agents like microorganisms. Many indigenous microorganisms in water and soil are capable of degrading hydrocarbon contaminants. This paper presents an updated overview of petroleum hydrocarbon degradation by microorganisms under different ecosystems. PMID:21350672

Organic-Inorganic Perovskites: Structural Versatility for Functional Materials Design.

PubMed

Saparov, Bayrammurad; Mitzi, David B

2016-04-13

Although known since the late 19th century, organic-inorganic perovskites have recently received extraordinary research community attention because of their unique physical properties, which make them promising candidates for application in photovoltaic (PV) and related optoelectronic devices. This review will explore beyond the current focus on three-dimensional (3-D) lead(II) halide perovskites, to highlight the great chemical flexibility and outstanding potential of the broader class of 3-D and lower dimensional organic-based perovskite family for electronic, optical, and energy-based applications as well as fundamental research. The concept of a multifunctional organic-inorganic hybrid, in which the organic and inorganic structural components provide intentional, unique, and hopefully synergistic features to the compound, represents an important contemporary target.

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-08-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, Cj*, by including water and other inorganics in the absorbing phase. Such a Cj* definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only.

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-05-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of the phase diagram. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, C*j, by including water and other inorganics in the absorbing phase. Such a C*j definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only.

Determination of volatile organic compounds from biowaste and co-fermentation biogas plants by single-sorbent adsorption.

PubMed

Salazar Gómez, J I; Lohmann, H; Krassowski, J

2016-06-01

Characterisation of biogases is normally dedicated to the online monitoring of the major components methane and carbon dioxide and, to a lesser extent, to the determination of ammonia and hydrogen sulphide. For the case of Volatile Organic Compounds (VOCs), much less attention is usually paid, since such compounds are normally removed during gas conditioning and with exception of sulphur compounds and siloxanes represent a rather low risk to conventional downstream devices but could be a hindrance for fuel cells. However, there is very little information in the literature about the type of substances found in biogases generated from biowaste or co-fermentation plants and their concentration fluctuations. The main aim of this study was to provide information about the time dependencies of the VOCs in three biogas plants spread out through Germany from autumn until summer, which have different process control, in order to assess their potential as biofuels. Additionally, this study was an attempt to establish a correlation between the nature of the substrates used in the biogas plants and the composition of the VOCs present in the gas phase. Significant time-dependent variations in concentration were observed for most VOCs but only small changes in composition were observed. In general, terpenes and ketones appeared as the predominant VOCs in biogas. Although for substances such as esters, sulphur-organic compounds and siloxanes the average concentrations observed were rather low, they exhibited significant concentration peaks. The second biogas plant which operates with dry fermentation was found to contain the highest levels of VOCs. The amount of total volatile organic compounds (TVOCs) for the first, second and third biogas plants ranged from 35 to 259 mg Nm(-3), 291-1731 mg Nm(-3) and 84-528 mg Nm(-3), respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electricity generation from food wastes and characteristics of organic matters in microbial fuel cell.

PubMed

Li, Hui; Tian, Yu; Zuo, Wei; Zhang, Jun; Pan, Xiaoyue; Li, Lipin; Su, Xinying

2016-04-01

The microbial fuel cell (MFC) was evaluated as an alternative way to recover electricity from canteen based food waste. Characteristics of the organics in food waste before and after the MFC treatment were analyzed to investigate how the organic matters were biodegraded and transformed during the MFC treatment. A maximum power density of 5.6W/m(3) and an average output voltage of 0.51V were obtained. During the MFC operation, the hydrophilic and acidic fractions were more readily degraded, compared to the neutral fractions. Additionally, aromatic compounds in the hydrophilic fraction were more preferentially removed than non-aromatic compounds. The MFC could easily remove the tryptophan protein-like substances in all fractions and aromatic proteins in hydrophilic and hydrophobic neutral fractions. Additionally, the hydrophobic amide-1 proteins and aliphatic components were readily hydrolyzed and biodegraded in the MFC. These findings may facilitate the pretreatment and posttreatment choices for MFC system fed with food waste. Copyright © 2016 Elsevier Ltd. All rights reserved.

Real-time detection of hazardous materials in air

NASA Astrophysics Data System (ADS)

Schechter, Israel; Schroeder, Hartmut; Kompa, Karl L.

1994-03-01

A new detection system has been developed for real-time analysis of organic compounds in ambient air. It is based on multiphoton ionization by an unfocused laser beam in a single parallel-plate device. Thus, the ionization volume can be relatively large. The amount of laser created ions is determined quantitatively from the induced total voltage drop between the biased plates (Q equals (Delta) V(DOT)C). Mass information is obtained from computer analysis of the time-dependent signal. When a KrF laser (5 ev) is used, most of the organic compounds can be ionized in a two-photon process, but none of the standard components of atmospheric air are ionized by this process. Therefore, this instrument may be developed as a `sniffer' for organic materials. The method has been applied for benzene analysis in air. The detection limit is about 10 ppb. With a simple preconcentration technique the detection limit can be decreased to the sub-ppb range. Simple binary mixtures are also resolved.

Radiation processing of organics and biological materials exposed to ocean world surface conditions.

NASA Astrophysics Data System (ADS)

Hand, K. P.; Carlson, R. W.

2017-12-01

Assessing the habitability of ocean worlds, such as Europa and Enceladus, motivates a search for endogenous carbon compounds that could be indicative of a habitable, or even inhabited, subsurface liquid water environment. We have examined the role of destruction and synthesis of organic compounds via 10 keV electron bombardment of ices generated under temperature and pressure conditions comparable to Europa and Enceladus. Short-chain organics and ammonia, in combination with water, were exposed to Mrad to Grad doses and observed to evolve to a `lost' carbon fraction (CO and CO2) and a `retained' carbon fraction (consisting of a highly refractory `ocean world tholin' populated by highly radiation resistant carbonyl, aldehyde, and nitrile components). The retained fraction is of key importance as this likely represents the observable fraction for future spacecraft investigations. We also irradiated microbial spores (B. pumilis) to approximately 2 Grad and have found persistence of biomolecule fractions derived from proteins and nucleic acids.

The Denver Aerosol Sources and Health (DASH) Study: Overview and Early Findings

PubMed Central

Vedal, S.; Hannigan, M.P.; Dutton, S.J.; Miller, S. L.; Milford, J.B.; Rabinovitch, N.; Kim, S.-Y.; Sheppard, L.

2012-01-01

Improved understanding of the sources of air pollution that are most harmful could aid in developing more effective measures for protecting human health. The Denver Aerosol Sources and Health (DASH) study was designed to identify the sources of ambient fine particulate matter (PM2.5) that are most responsible for the adverse health effects of short-term exposure to PM 2.5. Daily 24-hour PM2.5 sampling began in July 2002 at a residential monitoring site in Denver, Colorado, using both Teflon and quartz filter samplers. Sampling is planned to continue through 2008. Chemical speciation is being carried out for mass, inorganic ionic compounds (sulfate, nitrate and ammonium), and carbonaceous components, including elemental carbon, organic carbon, temperature-resolved organic carbon fractions and a large array of organic compounds. In addition, water soluble metals were measured daily for 12 months in 2003. A receptor-based source apportionment approach utilizing positive matrix factorization (PMF) will be used to identify PM 2.5 source contributions for each 24-hour period. Based on a preliminary assessment using synthetic data, the proposed source apportionment should be able to identify many important sources on a daily basis, including secondary ammonium nitrate and ammonium sulfate, diesel vehicle exhaust, road dust, wood combustion and vegetative debris. Meat cooking, gasoline vehicle exhaust and natural gas combustion were more challenging for PMF to accurately identify due to high detection limits for certain organic molecular marker compounds. Measurements of these compounds are being improved and supplemented with additional organic molecular marker compounds. The health study will investigate associations between daily source contributions and an array of health endpoints, including daily mortality and hospitalizations and measures of asthma control in asthmatic children. Findings from the DASH study, in addition to being of interest to policymakers, by identifying harmful PM2.5 sources may provide insights into mechanisms of PM effect. PMID:22723735

The Denver Aerosol Sources and Health (DASH) study: Overview and early findings

NASA Astrophysics Data System (ADS)

Vedal, S.; Hannigan, M. P.; Dutton, S. J.; Miller, S. L.; Milford, J. B.; Rabinovitch, N.; Kim, S.-Y.; Sheppard, L.

Improved understanding of the sources of air pollution that are most harmful could aid in developing more effective measures for protecting human health. The Denver Aerosol Sources and Health (DASH) study was designed to identify the sources of ambient fine particulate matter (PM 2.5) that are most responsible for the adverse health effects of short-term exposure to PM 2.5. Daily 24-h PM 2.5 sampling began in July 2002 at a residential monitoring site in Denver, Colorado, using both Teflon and quartz filter samplers. Sampling is planned to continue through 2008. Chemical speciation is being carried out for mass, inorganic ionic compounds (sulfate, nitrate and ammonium), and carbonaceous components, including elemental carbon, organic carbon, temperature-resolved organic carbon fractions and a large array of organic compounds. In addition, water-soluble metals were measured daily for 12 months in 2003. A receptor-based source apportionment approach utilizing positive matrix factorization (PMF) will be used to identify PM 2.5 source contributions for each 24-h period. Based on a preliminary assessment using synthetic data, the proposed source apportionment should be able to identify many important sources on a daily basis, including secondary ammonium nitrate and ammonium sulfate, diesel vehicle exhaust, road dust, wood combustion and vegetative debris. Meat cooking, gasoline vehicle exhaust and natural gas combustion were more challenging for PMF to accurately identify due to high detection limits for certain organic molecular marker compounds. Measurements of these compounds are being improved and supplemented with additional organic molecular marker compounds. The health study will investigate associations between daily source contributions and an array of health endpoints, including daily mortality and hospitalizations and measures of asthma control in asthmatic children. Findings from the DASH study, in addition to being of interest to policymakers, by identifying harmful PM 2.5 sources may provide insights into mechanisms of PM effect.

Geochemical Fate and Transport of Sildenafil and Vardenafil

NASA Astrophysics Data System (ADS)

Richter, L.; Boudinot, G.; Vulava, V. M.; Cory, W. C.

2015-12-01

The geochemical fate of pharmaceuticals and their degradation products is a developing environmental field. The geologic, chemical, and biological fate of these pollutants has become very relevant with the increase in human population and the resulting increase in pollutant concentrations in the environment. In this study, we focus on sildenafil (SDF) and vardenafil (VDF), active compounds in Viagra and Levitra, respectively, two commonly used erectile dysfunction drugs. The main objective is to determine the sorption potential and transport behavior of these two compounds in natural soils. Both SDF and VDF are complex organic molecules with multiple amine functional groups in their structures. Two types of natural acidic soils (pH≈4.5), an organic-rich soil (7.6% OM) and clay-rich soil (5.1% clay) were used in this study to determine which soil components influence sorption behavior of both compounds. Sorption isotherms measured using batch reactors were nearly linear, but sorption was stronger in soil that contained higher clay content. Both compounds have multiple pKas due to the amine functional groups, the relevant pKas of SDF are 5.97 and 7.27, and those of VDF's are 4.72 and 6.21. These values indicate that these compounds likely behave as cations in soil suspensions and hence were strongly sorbed to negatively-charged clay minerals present in both soils. The clay composition in both soils is predominantly kaolinite with smaller amount of montmorillonite, both of which have a predominantly negative surface charge. Transport experiments using glass chromatography columns indicated that both compounds were more strongly retarded in the clay-rich soils. Breakthrough curves from the transport experiments were modeled using convection-dispersion transport equations. The organic matter in the soil seemed to play a less dominant role in the geochemistry in this study, but is likely to transform both compounds into derivative compounds as seen in other studies.

Dehydrogenation of liquid fuel in microchannel catalytic reactor

DOEpatents

Toseland, Bernard Allen; Pez, Guido Peter; Puri, Pushpinder Singh

2010-08-03

The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

Dehydrogenation of liquid fuel in microchannel catalytic reactor

DOEpatents

Toseland, Bernard Allen [Allentown, PA; Pez, Guido Peter [Allentown, PA; Puri, Pushpinder Singh [Emmaus, PA

2009-02-03

The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

Photoacoustic study on the possible components of total suspended particles

NASA Astrophysics Data System (ADS)

Wang, Xidong; Huang, Zuohua; Tang, Zhilie

2006-02-01

Total suspended particles (TSP) are one of the main atmospheric pollutants. The ingredients are very complex, mainly including black carbon (C),organic compound, inorganic compound and biologic component, which will do great harm to human's health. During environmental monitoring, the airborne suspended particle always is an index for evaluating the quality of atmosphere. In this article, possible mixture of TSP is proposed to determine its ingredients and content by photoacoustic spectroscopy. The normalized photoacoustic (PA) signal of the sulfur powder, mixtures of sulfur and black carbon in different proportions are obtained respectively. Simulation with linear equation says that the PA signal has a certain relationship with the content of sample. The normalized PA spectroscopy of various materials is acquired via examining the sample of the powder of cupric sulfate mixed with nitro compound (2, 5 -methoxybenzoic-4nitro-dehyde), Portland cement, residual particles of automobile exhaust pipe, ash of power plant's stocks. The experimental results have important reference value to the practical analysis of TSP, it also provides new possible methodology to the environmental monitoring.

Defense Acquisitions Acronyms and Terms

DTIC Science & Technology

2012-12-01

Computer-Aided Design CADD Computer-Aided Design and Drafting CAE Component Acquisition Executive; Computer-Aided Engineering CAIV Cost As an...Radiation to Ordnance HFE Human Factors Engineering HHA Health Hazard Assessment HNA Host-Nation Approval HNS Host-Nation Support HOL High -Order...Engineering Change Proposal VHSIC Very High Speed Integrated Circuit VLSI Very Large Scale Integration VOC Volatile Organic Compound W WAN Wide

Selective Detection of Target Volatile Organic Compounds in Contaminated Humid Air Using a Sensor Array with Principal Component Analysis

PubMed Central

Itoh, Toshio; Akamatsu, Takafumi; Tsuruta, Akihiro; Shin, Woosuck

2017-01-01

We investigated selective detection of the target volatile organic compounds (VOCs) nonanal, n-decane, and acetoin for lung cancer-related VOCs, and acetone and methyl i-butyl ketone for diabetes-related VOCs, in humid air with simulated VOC contamination (total concentration: 300 μg/m3). We used six “grain boundary-response type” sensors, including four commercially available sensors (TGS 2600, 2610, 2610, and 2620) and two Pt, Pd, and Au-loaded SnO2 sensors (Pt, Pd, Au/SnO2), and two “bulk-response type” sensors, including Zr-doped CeO2 (CeZr10), i.e., eight sensors in total. We then analyzed their sensor signals using principal component analysis (PCA). Although the six “grain boundary-response type” sensors were found to be insufficient for selective detection of the target gases in humid air, the addition of two “bulk-response type” sensors improved the selectivity, even with simulated VOC contamination. To further improve the discrimination, we selected appropriate sensors from the eight sensors based on the PCA results. The selectivity to each target gas was maintained and was not affected by contamination. PMID:28753948

On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) medical applications, food control and environmental research

NASA Astrophysics Data System (ADS)

Lindinger, W.; Hansel, A.; Jordan, A.

1998-02-01

A proton transfer reaction mass spectrometer (PTR-MS) system has been developed which allows for on-line measurements of trace components with concentrations as low as a few pptv. The method is based on reactions of H3O+ ions, which perform non-dissociative proton transfer to most of the common volatile organic compounds (VOCs) but do not react with any of the components present in clean air. Medical applications by means of breath analysis allow for monitoring of metabolic processes in the human body, and examples of food research are discussed on the basis of VOC emissions from fruit, coffee and meat. Environmental applications include investigations of VOC emissions from decaying biomatter which have been found to be an important source for tropospheric acetone, methanol and ethanol. On-line monitoring of the diurnal variations of VOCs in the troposphere yield data demonstrating the present sensitivity of PTR-MS to be in the range of a few pptv. Finally, PTR-MS has proven to be an ideal tool to measure Henry's law constants and their dependencies on temperature as well as on the salt content of water.

Screening of the key volatile organic compounds of Tuber melanosporum fermentation by aroma sensory evaluation combination with principle component analysis

PubMed Central

Liu, Rui-Sang; Jin, Guang-Huai; Xiao, Deng-Rong; Li, Hong-Mei; Bai, Feng-Wu; Tang, Ya-Jie

2015-01-01

Aroma results from the interplay of volatile organic compounds (VOCs) and the attributes of microbial-producing aromas are significantly affected by fermentation conditions. Among the VOCs, only a few of them contribute to aroma. Thus, screening and identification of the key VOCs is critical for microbial-producing aroma. The traditional method is based on gas chromatography-olfactometry (GC-O), which is time-consuming and laborious. Considering the Tuber melanosporum fermentation system as an example, a new method to screen and identify the key VOCs by combining the aroma evaluation method with principle component analysis (PCA) was developed in this work. First, an aroma sensory evaluation method was developed to screen 34 potential favorite aroma samples from 504 fermentation samples. Second, PCA was employed to screen nine common key VOCs from these 34 samples. Third, seven key VOCs were identified by the traditional method. Finally, all of the seven key VOCs identified by the traditional method were also identified, along with four others, by the new strategy. These results indicate the reliability of the new method and demonstrate it to be a viable alternative to the traditional method. PMID:26655663

Bioavailability of Heavy Metals in Soil: Impact on Microbial Biodegradation of Organic Compounds and Possible Improvement Strategies

PubMed Central

Olaniran, Ademola O.; Balgobind, Adhika; Pillay, Balakrishna

2013-01-01

Co-contamination of the environment with toxic chlorinated organic and heavy metal pollutants is one of the major problems facing industrialized nations today. Heavy metals may inhibit biodegradation of chlorinated organics by interacting with enzymes directly involved in biodegradation or those involved in general metabolism. Predictions of metal toxicity effects on organic pollutant biodegradation in co-contaminated soil and water environments is difficult since heavy metals may be present in a variety of chemical and physical forms. Recent advances in bioremediation of co-contaminated environments have focussed on the use of metal-resistant bacteria (cell and gene bioaugmentation), treatment amendments, clay minerals and chelating agents to reduce bioavailable heavy metal concentrations. Phytoremediation has also shown promise as an emerging alternative clean-up technology for co-contaminated environments. However, despite various investigations, in both aerobic and anaerobic systems, demonstrating that metal toxicity hampers the biodegradation of the organic component, a paucity of information exists in this area of research. Therefore, in this review, we discuss the problems associated with the degradation of chlorinated organics in co-contaminated environments, owing to metal toxicity and shed light on possible improvement strategies for effective bioremediation of sites co-contaminated with chlorinated organic compounds and heavy metals. PMID:23676353

Acute toxicity of leachates of tire wear material to Daphnia magna--variability and toxic components.

PubMed

Wik, Anna; Dave, Göran

2006-09-01

Large amounts of tire rubber are deposited along the roads due to tread wear. Several compounds may leach from the rubber and cause toxicity to aquatic organisms. To investigate the toxic effects of tire wear material from different tires, rubber was abraded from the treads of twenty-five tires. Leachates were prepared by allowing the rubber to equilibrate with dilution water at 44 degrees C for 72 h. Then the rubber was filtered from the leachates, and test organisms (Daphnia magna) were added. Forty-eight hour EC50s ranged from 0.5 to >10.0 g l(-1). The toxicity identification evaluation (TIE) indicated that non-polar organic compounds caused most of the toxicity. UV exposure of the filtered tire leachates caused no significant increase in toxicity. However, when tested as unfiltered leachates (the rubber was not filtered from the leachates before addition of D. magna) photo-enhanced toxicity was considerable for some tires, which means that test procedures are important when testing tire leachates for aquatic (photo) toxicity. The acute toxicity of tire wear for Daphnia magna was found to be <40 times a predicted environmental concentration based on reports on the concentration of a tire component found in environmental samples, which emphasizes the need for a more extensive risk assessment of tire wear for the environment.

Benzoic Acid and Chlorobenzoic Acids: Thermodynamic Study of the Pure Compounds and Binary Mixtures With Water.

PubMed

Reschke, Thomas; Zherikova, Kseniya V; Verevkin, Sergey P; Held, Christoph

2016-03-01

Benzoic acid is a model compound for drug substances in pharmaceutical research. Process design requires information about thermodynamic phase behavior of benzoic acid and its mixtures with water and organic solvents. This work addresses phase equilibria that determine stability and solubility. In this work, Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) was used to model the phase behavior of aqueous and organic solutions containing benzoic acid and chlorobenzoic acids. Absolute vapor pressures of benzoic acid and 2-, 3-, and 4-chlorobenzoic acid from literature and from our own measurements were used to determine pure-component PC-SAFT parameters. Two binary interaction parameters between water and/or benzoic acid were used to model vapor-liquid and liquid-liquid equilibria of water and/or benzoic acid between 280 and 413 K. The PC-SAFT parameters and 1 binary interaction parameter were used to model aqueous solubility of the chlorobenzoic acids. Additionally, solubility of benzoic acid in organic solvents was predicted without using binary parameters. All results showed that pure-component parameters for benzoic acid and for the chlorobenzoic acids allowed for satisfying modeling phase equilibria. The modeling approach established in this work is a further step to screen solubility and to predict the whole phase region of mixtures containing pharmaceuticals. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Pinonaldehyde and some other organics in rain and snow in central Japan.

PubMed

Satsumabayashi, H; Nishizawa, H; Yokouchi, Y; Ueda, H

2001-11-01

Solvent-extractable organic compounds in the rain and snow collected at local cities in the mountainous region in central Japan, were analyzed by GC/MS and GC. Pinonaldehyde (2,2-dimethyl-3-acetyl-cyclobutyl-ethanal), an atmospheric reaction product of alpha-pinene, was detected in the rain and snow for the first time, and n-alkanes (C17-C33), fatty acids (C8-C23), and benzoic acid were also detected as major organic components. Concentrations of pinonaldehyde, C17-C33 n-alkanes, C8-C11 fatty acids, C12-C23 fatty acids and benzoic acid ranged between <0.02-13, 0.10-35, 0.55-5.7, 4.2-19 and <0.02-6.0 microg/l, respectively. Their composition showed some difference in summer and winter. In summer, fatty acids and benzoic acid were more abundant, while pinonaldehyde and n-alkanes were much less. Higher photochemical reactivity and higher bioactivity in summer could explain these seasonal changes except for pinonaldehyde, which would suffer from further oxidation in the atmosphere after its photochemical production from alpha-pinene. Predominance of pinonaldehyde and C12-C23 fatty acids in the rain and snow showed a remarkable contrast to n-alkanes in aerosol phase, which were the most abundant components. It indicated that oxygenated products from biogenic compounds might be important as cloud condensation nuclei in forest areas.

Identification of Organic Sulfate Esters in d-Limonene Ozonolysis SOA Under Acidic Condition

NASA Astrophysics Data System (ADS)

Iinuma, Y.; Mueller, C.; Boege, O.; Herrmann, H.

2006-12-01

Secondary organic aerosol (SOA) components from gas phase ozonolysis of d-limonene were investigated in a series of indoor chamber experiments. The compounds smaller than 300 Da were quantified using capillary electrophoresis coupled to electrospray ionisation ion trap mass spectrometry (CE/ESI-ITMS). HPLC coupled to an ESI-TOFMS and an ESI-ITMS was used for structural study of dimmers and oligomers. Only 10% of the produced SOA could be attributed to low molecular weight carboxylic acids (Mw<300). The oxidation products which have molecular weights over 300 were detected regardless of the seed particle acidity but the concentrations of these compounds were much higher for acidic seed particle experiments. Strong signals of the compounds with mass to charge ratios (m/z) 281, 465 and 481 were detected when sulphuric acid was used in the seed particles. These compounds showed a strong fragment of m/z 97 in MS2 or MS3 spectra indicating the presence of sulfate in the structures. HPLC/ESI-TOFMS analysis suggests the elemental compositions of C10H17O7S-, C20H33O10S- and C20H33O11S- for m/z 281, 465 and 481, respectively. Based on MS^{n} and TOFMS results, they are most likely organic sulfate esters, possibly formed by a heterogeneous acid catalyzed reaction of a limonene oxidation product and sulfuric acid in the particle phase. The concentrations of the organic sulfate ester were as high as 3.7 μgm-3 for m/z 281.

Current understandings and perspectives on non-cancer health effects of benzene: A global concern

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

Bahadar, Haji; Pharmaceutical Sciences Research Center and Faculty of Pharmacy, Tehran University of Medical Sciences; Mostafalou, Sara

Objective: Benzene, as a volatile organic compound, is known as one of the main air pollutants in the environment. The aim of this review is to summarize all available evidences on non-cancerous health effects of benzene providing an overview of possible association of exposure to benzene with human chronic diseases, specially, in those regions of the world where benzene concentration is being poorly monitored. Methodology: A bibliographic search of scientific databases including PubMed, Google Scholar, and Scirus was conducted with key words of “benzene toxic health effects”, “environmental volatile organic compounds”, “diabetes mellitus and environmental pollutants”, “breast cancer and environmentalmore » pollution”, “prevalence of lung cancer”, and “diabetes prevalence”. More than 300 peer reviewed papers were examined. Experimental and epidemiologic studies reporting health effects of benzene and volatile organic compounds were included in the study. Results: Epidemiologic and experimental studies suggest that benzene exposure can lead to numerous non-cancerous health effects associated with functional aberration of vital systems in the body like reproductive, immune, nervous, endocrine, cardiovascular, and respiratory. Conclusion: Chronic diseases have become a health burden of global dimension with special emphasis in regions with poor monitoring over contents of benzene in petrochemicals. Benzene is a well known carcinogen of blood and its components, but the concern of benzene exposure is more than carcinogenicity of blood components and should be evaluated in both epidemiologic and experimental studies. Aspect of interactions and mechanism of toxicity in relation to human general health problems especially endocrine disturbances with particular reference to diabetes, breast and lung cancers should be followed up. - Highlights: • Benzene is a volatile organic compound and established blood carcinogen. • Exposure to benzene needs to be evaluated in related chronic diseases. • Cigarette smoke is the main source for indoor benzene exposure. • Health outcomes associated with air pollutants are poorly characterized due to lack of comprehensive monitoring system.« less

Evaluation and Prediction of Henry’s Law Constants and Aqueous Solubilities for Solvents and Hydrocarbon Fuel Components. Volume 1. Technical Discussion

DTIC Science & Technology

1987-09-01

spectrum cap with a Teflonýliner facing toward the bottle headspace. These liners are used only once to prevent adsorption of test compound into the...used to predict carbon adsorption of contaminants, and the air or steam stripping behavior for a given organic. For highly soluble materials these data...first of these stems from the organic-solute losses due to adsorption of the solute on the flask walls or to evaporation. This quantity is somewhat

Structural characteristics of fulvic acids from Continental Shelf sediments

USGS Publications Warehouse

Hatcher, P.G.; Breger, I.A.; Mattingly, M.A.

1980-01-01

Fulvic acids are those components of soil organic matter that remain soluble after a dilute alkaline extract of the soil is acidified to pH 2 (refs 1, 2). This extraction procedure has been applied to marine sediments, and the organic compounds so recovered have been called marine sedimentary fulvic acids. These fulvic acids are thought to form more complex humic substances in marine sediments by condensation reactions3. However, the chemical structural compositions of marine fulvic acids have not been defined sufficiently to allow this precursor relationship to be made. Here NMR spectroscopy is used to identify more clearly the chemical structural components of some marine sedimentary fulvic acids, thus enabling a more useful examination of their relationship to more complex humic substances. ?? 1980 Nature Publishing Group.

Development of solvent systems with room temperature ionic liquids for the countercurrent chromatographic separation of very nonpolar lipid compounds.

PubMed

Müller, Marco; Englert, Michael; Earle, Martyn J; Vetter, Walter

2017-03-10

Solvent systems are not readily available for the separation of very nonpolar compounds by countercurrent chromatography (CCC). In this study we therefore evaluated the suitability of room temperature ionic liquids (IL) in organic solvents for the CCC separation of the extremely nonpolar lipid compounds tripalmitin (PPP) and cholesteryl stearate (CS). The four IL tested were [C 10 mim][OTf], [C 2 mim][NTf 2 ], [P66614][NTf 2 ], and [P66614][Cl]. Search for a CCC-suited solvent system started with solubility studies with fourteen organic solvents. Following this, combinations were made with one organic solvent miscible and one organic solvent immiscible with IL (147 combinations). Twenty-four initially monophasic mixtures of two organic solvents became biphasic by adding IL. Several unexpected results could be observed. For instance, n-hexane and n-heptane became biphasic with [P66614][Cl]. Further nine systems became biphasic although the IL was not miscible in any of the two components. These 33 solvent systems were investigated with regard to phase ratio, settling time, share of IL in the upper phase and last not least the K U/L values of PPP and CS, which were 8.1 and 7.7 respectively. The most promising system, n-heptane/chloroform/[C 10 mim][OTf] (3:3:1, v/v/v) allowed a partial separation of PPP and CS by CCC which was not achieved beforehand. Copyright © 2017 Elsevier B.V. All rights reserved.

Fungal succession in relation to volatile organic compounds emissions from Scots pine and Norway spruce leaf litter-decomposing fungi

NASA Astrophysics Data System (ADS)

Isidorov, Valery; Tyszkiewicz, Zofia; Pirożnikow, Ewa

2016-04-01

Leaf litter fungi are partly responsible for decomposition of dead material, nutrient mobilization and gas fluxes in forest ecosystems. It can be assumed that microbial destruction of dead plant materials is an important source of volatile organic compounds (VOCs) emitted into the atmosphere from terrestrial ecosystems. However, little information is available on both the composition of fungal VOCs and their producers whose community can be changed at different stages of litter decomposition. The fungal community succession was investigated in a litter bag experiment with Scots pine (Pinus sylvestris) and Norway spruce (Picea abies) needle litter. The succession process can be divided into a several stages controlled mostly by changes in litter quality. At the very first stages of decomposition the needle litter was colonized by ascomycetes which can use readily available carbohydrates. At the later stages, the predominance of Trichoderma sp., the known producers of cellulolytic enzymes, was documented. To investigate the fungi-derived VOCs, eight fungi species were isolated. As a result of gas chromatographic analyses, as many as 75C2sbnd C15 fungal volatile compounds were identified. Most components detected in emissions were very reactive substances: the principal groups of VOCs were formed by monoterpenes, carbonyl compounds and aliphatic alcohols. It was found that production of VOCs by fungi is species specific: only 10 metabolites were emitted into the gas phase by all eight species. The reported data confirm that the leave litter decomposition is important source of reactive organic compounds under the forest canopy.

Uptake, biotransformation, and elimination of benzo[a]pyrene by the gammarid amphipod, Leptocheirus plumulosus

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

Dickbut, R.M.; Huszai, C.M.; Lay, P.W.

1995-12-31

The uptake, biotransformation, and elimination of {sup 3}H-benzo[a]pyrene (B[a]P) by the gammarid amphipod Leptocheirus plumulosus was evaluated in laboratory exposures. Rapid uptake (i.e. within 2.5 h) of sediment-associated B[a]P was observed, and during the exposures organism body burdens were dominated by organic extractable (e.g. parent compound) components, with aqueous soluble and bound metabolites constituting a much smaller fraction of the total body burden. However, upon discontinuation of exposure of the organisms to B[a]P, organic extractable compounds were more rapidly eliminated by L. plumulosus than the aqueous extractable and bound contaminant pools. Uptake and elimination of B[a]P were adequately modeled assumingmore » first order kinetics, with the exception of the early stages of exposure. The rapid uptake during the first few hours of exposure of Leptocheirus to sediment-associated B[a]P may be due to sorption of B[a]P to the exoskeleton of the organism. This hypothesis is under further investigation. Uptake and elimination of B[a]P metabolite pools by L. plumulosus was best modeled assuming a fraction of the metabolite pool was irreversibly bound or slowly eliminated.« less

Source Characterization of Volatile Organic Compounds Affecting the Air Quality in a Coastal Urban Area of South Texas

PubMed Central

Sanchez, Marciano; Karnae, Saritha; John, Kuruvilla

2008-01-01

Selected Volatile Organic Compounds (VOC) emitted from various anthropogenic sources including industries and motor vehicles act as primary precursors of ozone, while some VOC are classified as air toxic compounds. Significantly large VOC emission sources impact the air quality in Corpus Christi, Texas. This urban area is located in a semi-arid region of South Texas and is home to several large petrochemical refineries and industrial facilities along a busy ship-channel. The Texas Commission on Environmental Quality has setup two continuous ambient monitoring stations (CAMS 633 and 634) along the ship channel to monitor VOC concentrations in the urban atmosphere. The hourly concentrations of 46 VOC compounds were acquired from TCEQ for a comprehensive source apportionment study. The primary objective of this study was to identify and quantify the sources affecting the ambient air quality within this urban airshed. Principal Component Analysis/Absolute Principal Component Scores (PCA/APCS) was applied to the dataset. PCA identified five possible sources accounting for 69% of the total variance affecting the VOC levels measured at CAMS 633 and six possible sources affecting CAMS 634 accounting for 75% of the total variance. APCS identified natural gas emissions to be the major source contributor at CAMS 633 and it accounted for 70% of the measured VOC concentrations. The other major sources identified at CAMS 633 included flare emissions (12%), fugitive gasoline emissions (9%), refinery operations (7%), and vehicle exhaust (2%). At CAMS 634, natural gas sources were identified as the major source category contributing to 31% of the observed VOC. The other sources affecting this site included: refinery operations (24%), flare emissions (22%), secondary industrial processes (12%), fugitive gasoline emissions (8%) and vehicle exhaust (3%). PMID:19139530

Selection of nutrient used in biogenic healing agent for cementitious materials

NASA Astrophysics Data System (ADS)

Tziviloglou, Eirini; Wiktor, Virginie; Jonkers, Henk M.; Schlangen, Erik

2017-06-01

Biogenic self-healing cementitious materials target on the closure of micro-cracks with precipitated inorganic minerals originating from bacterial metabolic activity. Dormant bacterial spores and organic mineral compounds often constitute a biogenic healing agent. The current paper focuses on the investigation of the most appropriate organic carbon source to be used as component of a biogenic healing agent. It is of great importance to use an appropriate organic source, since it will firstly ensure an optimal bacterial performance in terms of metabolic activity, while it should secondly affect the least the properties of the cementitious matrix. The selection is made among three different organic compounds, namely calcium lactate, calcium acetate and sodium gluconate. The methodology that was used for the research was based on continuous and non-continuous oxygen consumption measurements of washed bacterial cultures and on compressive strength tests on mortar cubes. The oxygen consumption investigation revealed a preference for calcium lactate and acetate, but an indifferent behaviour for sodium gluconate. The compressive strength on mortar cubes with different amounts of either calcium lactate or acetate (up to 2.24% per cement weight) was not or it was positively affected when the compounds were dissolved in the mixing water. In fact, for calcium lactate the increase in compressive strength reached 8%, while for calcium acetate the maximum strength increase was 13.4%.

Natural variation in chemosensation: lessons from an island nematode

PubMed Central

McGaughran, Angela; Morgan, Katy; Sommer, Ralf J

2013-01-01

All organisms must interact with their environment, responding in behavioral, chemical, and other ways to various stimuli throughout their life cycles. Characterizing traits that directly represent an organism's ability to sense and react to their environment provides useful insight into the evolution of life-history strategies. One such trait for the nematode Pristionchus pacificus, chemosensation, is involved in navigation to beetle hosts. Essential for the survival of the nematode, chemosensory behavior may be subject to variation as nematodes discriminate among chemical cues to complete their life cycle. We examine this hypothesis using natural isolates of P. pacificus from La Réunion Island. We select strains from a variety of La Réunion beetle hosts and geographic locations and examine their chemoattraction response toward organic compounds, beetle washes, and live beetles. We find that nematodes show significant differences in their response to various chemicals and are able to chemotax to live beetles in a novel assay. Further, strains can discriminate among different cues, showing more similar responses toward beetle washes than to organic compounds in cluster analyses. However, we find that variance in chemoattraction response is not significantly associated with temperature, location, or beetle host. Rather, strains show a more concerted response toward compounds they most likely directly encounter in the wild. We suggest that divergence in odor-guided behavior in P. pacificus may therefore have an important ecological component. PMID:24455150

[Estimate of the formation potential of secondary organic aerosol in Beijing summertime].

PubMed

Lü, Zi-Feng; Hao, Ji-Ming; Duan, Jing-Chun; Li, Jun-Hua

2009-04-15

Fractional aerosol coefficients (FAC) are used in conjunction with measurements of volatile organic compounds (VOC) during ozone episodes to estimate the formation potential of secondary organic aerosols (SOA) in the summertime of Beijing. The estimation is based on the actual atmospheric conditions of Beijing, and benzene and isoprene are considered as the precursors of SOA. The results show that 31 out of 70 measured VOC species are SOA precursors, and the total potential SOA formation is predicted to be 8.48 microg/m3, which accounts for 30% of fine organic particle matter. Toluene, xylene, pinene, ethylbenzene and n-undecane are the 5 largest contributors to SOA production and account for 20%, 22%, 14%, 9% and 4% of total SOA production, respectively. The anthropogenic aromatic compounds, which yield 76% of the calculated SOA, are the major source of SOA. The biogenic alkenes, alkanes and carbonyls produce 16%, 7% and 1% of SOA formation, respectively. The major components of produced SOA are expected to be aromatic compounds, aliphatic acids, carbonyls and aliphatic nitrates, which contribute to 72%, 14%, 11% and 3% of SOA mass, respectively. The SOA precursors have relatively low atmospheric concentrations and low ozone formation potential. Hence, SOA formation potential of VOC species, in addition to their atmospheric concentrations and ozone formation potential, should be considered in policy making process of VOCs control.

NAD+ Is a Food Component That Promotes Exit from Dauer Diapause in Caenorhabditis elegans.

PubMed

Mylenko, Mykola; Boland, Sebastian; Penkov, Sider; Sampaio, Julio L; Lombardot, Benoit; Vorkel, Daniela; Verbavatz, Jean-Marc; Kurzchalia, Teymuras V

2016-01-01

The free-living soil nematode Caenorhabditis elegans adapts its development to the availability of food. When food is scarce and population density is high, worms enter a developmentally arrested non-feeding diapause stage specialized for long-term survival called the dauer larva. When food becomes available, they exit from the dauer stage, resume growth and reproduction. It has been postulated that compound(s) present in food, referred to as the "food signal", promote exit from the dauer stage. In this study, we have identified NAD+ as a component of bacterial extract that promotes dauer exit. NAD+, when dissolved in alkaline medium, causes opening of the mouth and ingestion of food. We also show that to initiate exit from the dauer stage in response to NAD+ worms require production of serotonin. Thus, C. elegans can use redox cofactors produced by dietary organisms to sense food.

Identification and field evaluation of non-host volatiles disturbing host location by the tea geometrid, Ectropis obliqua.

PubMed

Zhang, Zheng-qun; Sun, Xiao-ling; Xin, Zhao-jun; Luo, Zong-xiu; Gao, Yu; Bian, Lei; Chen, Zong-mao

2013-10-01

Volatile organic compounds derived from non-host plants, Ocimum basilicum, Rosmarinus officinalis, Corymbia citriodora, and Ruta graveolens, can be used to mask host plant odors, and are repellent to the tea geometrid, Ectropis obliqua. Volatile compounds were collected by headspace absorption, and the components were identified and quantified by using gas chromatography/mass spectrometry. The responses of antennae of female E. obliqua to the compounds were evaluated with gas chromatography/electroantennography detection. Qualitative and quantitative differences were found among the four odor profiles. Consistent electroantennographic activity was obtained for eight of the volatiles from the four plants: β-myrcene, α-terpinene, γ-terpinene, linalool, cis-verbenol, camphor, α-terpineol, and verbenone. In a Y-tube bioassay, six chemicals, β-myrcene, γ-terpinene, (R)-(-)-linalool, (S)-(-)-cis-verbenol, (R)-(+)-camphor, and (S)-(-)-verbenone, were the main compounds responsible for repelling E. obliqua. An eight-component mixture including all of the bioactive compounds (in a ratio of 13:2:13:8:1:24:6:17) from R. officinalis was significantly more effective at repelling the moths than any single compound or a mixture of equal amounts of the eight compounds. Field results demonstrated that intercropping tea plants with R. officinalis effectively suppressed E. obliqua infestations in a tea plantation. Our findings suggests that odor blends of R. officinalis play a role in disturbing host orientation behavior, and in repelling E. obliqua adults, and that R. officinalis should be considered when developing "push-pull" strategies aimed at optimizing the control of E. obliqua with semiochemicals.

Understanding the molecular behavior of organotin compounds to design their effective use as agrochemicals: exploration via quantum chemistry and experiments.

PubMed

Ramalho, Teodorico C; Rocha, Marcus V J; da Cunha, Elaine F F; Oliveira, Luiz C A; Carvalho, Kele T C

2010-10-01

The high frequency of contamination by herbicides suggests the need for more active and selective agrochemicals. Organotin compounds are the active component of some herbicides, such as Du-Ter and Brestan, which is also a potent inhibitor of the F1Fo ATP Synthase. That is a key enzyme, because the ATP production is one of the major chemical reactions in living organisms. Thus ATP Synthase is regarded as a prime target for organotin compounds. In this line, molecular modeling studies and DFT calculations were performed in order to understand the molecular behavior of those compounds in solution. In addition, we investigated the reaction mechanism by ESI-MS analyses of the diphenyltin dichloride. Our findings indicate that an unstable key-intermediate generated in situ might take place in the reaction with ATP Synthase.

Isolation and Antifouling Activity of Azulene Derivatives from the Antarctic Gorgonian Acanthogorgia laxa.

PubMed

Patiño Cano, Laura P; Quintana Manfredi, Rodrigo; Pérez, Miriam; García, Mónica; Blustein, Guillermo; Cordeiro, Ralf; Pérez, Carlos D; Schejter, Laura; Palermo, Jorge A

2018-01-01

Three azulenoid sesquiterpenes (1 - 3) were isolated from the Antarctic gorgonian Acanthogorgia laxa collected by bottom trawls at -343 m. Besides linderazulene (1), and the known ketolactone 2, a new brominated C 16 linderazulene derivative (3) was also identified. This compound has an extra carbon atom at C(7) of the linderazulene framework. The antifouling activity of compounds 1 and 2 was assayed in the laboratory with Artemia salina larvae, and also in field tests, by incorporation in soluble-matrix experimental antifouling paints. The results obtained after a 45 days field trial of the paints, showed that compounds 1 and 2 displayed good antifouling potencies against a wide array of organisms. Compound 3, a benzylic bromide, was unstable and for this reason was not submitted to bioassays. Two known cembranolides: pukalide and epoxypukalide, were also identified as minor components of the extract. © 2018 Wiley-VHCA AG, Zurich, Switzerland.

Effect of supercritical carbon dioxide decaffeination on volatile components of green teas.

PubMed

Lee, S; Park, M K; Kim, K H; Kim, Y-S

2007-09-01

Volatile components in regular and decaffeinated green teas were isolated by simultaneous steam distillation and solvent extraction (SDE), and then analyzed by GC-MS. A total of 41 compounds, including 8 alcohols, 15 terpene-type compounds, 10 carbonyls, 4 N-containing compounds, and 4 miscellaneous compounds, were found in regular and decaffeinated green teas. Among them, linalool and phenylacetaldehyde were quantitatively dominant in both regular and decaffeinated green teas. By a decaffeination process using supercritical carbon dioxide, most volatile components decreased. The more caffeine was removed, the more volatile components were reduced in green teas. In particular, relatively nonpolar components such as terpene-type compounds gradually decreased according to the decaffeination process. Aroma-active compounds in regular and decaffeinated green teas were also determined and compared by aroma extract dilution analysis (AEDA). Most greenish and floral flavor compounds such as hexanal, (E)-2-hexenal, and some unknown compounds disappeared or decreased after the decaffeination process.

Mixture effects in samples of multiple contaminants - An inter-laboratory study with manifold bioassays.

PubMed

Altenburger, Rolf; Scholze, Martin; Busch, Wibke; Escher, Beate I; Jakobs, Gianina; Krauss, Martin; Krüger, Janet; Neale, Peta A; Ait-Aissa, Selim; Almeida, Ana Catarina; Seiler, Thomas-Benjamin; Brion, François; Hilscherová, Klára; Hollert, Henner; Novák, Jiří; Schlichting, Rita; Serra, Hélène; Shao, Ying; Tindall, Andrew; Tolefsen, Knut-Erik; Umbuzeiro, Gisela; Williams, Tim D; Kortenkamp, Andreas

2018-05-01

Chemicals in the environment occur in mixtures rather than as individual entities. Environmental quality monitoring thus faces the challenge to comprehensively assess a multitude of contaminants and potential adverse effects. Effect-based methods have been suggested as complements to chemical analytical characterisation of complex pollution patterns. The regularly observed discrepancy between chemical and biological assessments of adverse effects due to contaminants in the field may be either due to unidentified contaminants or result from interactions of compounds in mixtures. Here, we present an interlaboratory study where individual compounds and their mixtures were investigated by extensive concentration-effect analysis using 19 different bioassays. The assay panel consisted of 5 whole organism assays measuring apical effects and 14 cell- and organism-based bioassays with more specific effect observations. Twelve organic water pollutants of diverse structure and unique known modes of action were studied individually and as mixtures mirroring exposure scenarios in freshwaters. We compared the observed mixture effects against component-based mixture effect predictions derived from additivity expectations (assumption of non-interaction). Most of the assays detected the mixture response of the active components as predicted even against a background of other inactive contaminants. When none of the mixture components showed any activity by themselves then the mixture also was without effects. The mixture effects observed using apical endpoints fell in the middle of a prediction window defined by the additivity predictions for concentration addition and independent action, reflecting well the diversity of the anticipated modes of action. In one case, an unexpectedly reduced solubility of one of the mixture components led to mixture responses that fell short of the predictions of both additivity mixture models. The majority of the specific cell- and organism-based endpoints produced mixture responses in agreement with the additivity expectation of concentration addition. Exceptionally, expected (additive) mixture response did not occur due to masking effects such as general toxicity from other compounds. Generally, deviations from an additivity expectation could be explained due to experimental factors, specific limitations of the effect endpoint or masking side effects such as cytotoxicity in in vitro assays. The majority of bioassays were able to quantitatively detect the predicted non-interactive, additive combined effect of the specifically bioactive compounds against a background of complex mixture of other chemicals in the sample. This supports the use of a combination of chemical and bioanalytical monitoring tools for the identification of chemicals that drive a specific mixture effect. Furthermore, we demonstrated that a panel of bioassays can provide a diverse profile of effect responses to a complex contaminated sample. This could be extended towards representing mixture adverse outcome pathways. Our findings support the ongoing development of bioanalytical tools for (i) compiling comprehensive effect-based batteries for water quality assessment, (ii) designing tailored surveillance methods to safeguard specific water uses, and (iii) devising strategies for effect-based diagnosis of complex contamination. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Organic Analysis in Miller Range 090657 and Buckley Island 10933 CR2 Chondrites: Part 1 In-Situ Observation of Carbonaceous Material

NASA Technical Reports Server (NTRS)

Cao, T.; Nakamura-Messenger, K.; Berger, E. L.; Burton, A. S.; Messenger, S.; Clemett, S. J.

2016-01-01

Primitive carbonaceous chondrites contain a wide variety of organic material, ranging from soluble discrete molecules to insoluble unstructured kerogen-like component as well as structured nano-globules of macromolecular carbon. The relationship between the soluble organic molecules, macromolecular organic material, and host minerals are poorly understood. Due to the differences in extractability of soluble and insoluble organic materials, the analysis methods for each differ and are often performed independently. The combination of soluble and insoluble analyses, when performed concurrently, can provide a wider understanding on spatial distribution, and elemental, structural and isotopic composition of organic material in primitive meteorites. Furthermore, they can provide broader perspective on how extraterrestrial organic ma-terials potentially contributed to the synthesis of life's essential compounds such as amino acids, sugar acids, activated phosphates and nucleobases.

Discovery of a Pederin Family Compound in a Nonsymbiotic Bloom-Forming Cyanobacterium.

PubMed

Kust, Andreja; Mareš, Jan; Jokela, Jouni; Urajová, Petra; Hájek, Jan; Saurav, Kumar; Voráčová, Kateřina; Fewer, David P; Haapaniemi, Esa; Permi, Perttu; Řeháková, Klára; Sivonen, Kaarina; Hrouzek, Pavel

2018-05-18

The pederin family includes a number of bioactive compounds isolated from symbiotic organisms of diverse evolutionary origin. Pederin is linked to beetle-induced dermatitis in humans, and pederin family members possess potent antitumor activity caused by selective inhibition of the eukaryotic ribosome. Their biosynthesis is accomplished by a polyketide/nonribosomal peptide synthetase machinery employing an unusual trans-acyltransferase mechanism. Here, we report a novel pederin type compound, cusperin, from the free-living cyanobacterium Cuspidothrix issatschenkoi (earlier Aphanizomenon). The chemical structure of cusperin is similar to that of nosperin recently isolated from the lichen cyanobiont Nostoc sharing the tehrahydropyran moiety and major part of the linear backbone. However, the cusperin molecule is extended by a glycine residue and lacks one hydroxyl substituent. Pederins were previously thought to be exclusive to symbiotic relationships. However, C. issatschenkoi is a nonsymbiotic planktonic organism and a frequent component of toxic water blooms. Cusperin is devoid of the cytotoxic activity reported for other pederin family members. Hence, our findings raise questions about the role of pederin analogues in cyanobacteria and broaden the knowledge of ecological distribution of this group of polyketides.

Origin of inorganic and organic components of PM2.5 in subway stations of Barcelona, Spain.

PubMed

Martins, Vânia; Moreno, Teresa; Minguillón, María Cruz; van Drooge, Barend L; Reche, Cristina; Amato, Fulvio; de Miguel, Eladio; Capdevila, Marta; Centelles, Sonia; Querol, Xavier

2016-01-01

The present work assesses indoor air quality in stations of the Barcelona subway system. PM2.5 concentrations on the platforms of 4 subway stations were measured during two different seasons and the chemical composition was determined. A Positive Matrix Factorization analysis was performed to identify and quantify the contributions of major PM2.5 sources in the subway stations. Mean PM2.5 concentrations varied according to the stations design and seasonal periods. PM2.5 was composed of haematite, carbonaceous aerosol, crustal matter, secondary inorganic compounds, trace elements, insoluble sulphate and halite. Organic compounds such as PAHs, nicotine, levoglucosan and aromatic musk compounds were also identified. Subway PM2.5 source comprised emissions from rails, wheels, catenaries, brake pads and pantographs. The subway source showed different chemical profiles for each station, but was always dominated by Fe. Control actions on the source are important for the achievement of better air quality in the subway environment. Copyright © 2015 The Authors. Published by Elsevier Ltd.. All rights reserved.

Molecular-level characterization of reactive and refractory dissolved natural organic nitrogen compounds by atmospheric pressure photoionization coupled to Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Osborne, Daniel M; Podgorski, David C; Bronk, Deborah A; Roberts, Quinn; Sipler, Rachel E; Austin, David; Bays, James S; Cooper, William T

2013-04-30

Dissolved organic nitrogen (DON) represents a significant fraction of the total dissolved nitrogen pool in most surface waters and serves as an important nitrogen source for phytoplankton and bacteria. As with other natural organic matter mixtures, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) is the only technique currently able to provide molecular composition information on DON. Although electrospray ionization (ESI) is the most commonly used ionization method, it is not very efficient at ionizing most DON components. Positive- and negative-mode atmospheric pressure photoionization (APPI) coupled with ultrahigh resolution FTICRMS at 9.4 T were compared for determining the composition of DON before and after bioassays. Toluene was added as the APPI dopant to the solid-phase DON extracts, producing a final sample that was 90% methanol and 10% toluene by volume. Positive-mode (+) APPI proved significantly more efficient at ionizing DON; 62% of the formulas that could be assigned in the positive-ion spectrum contained at least one nitrogen atom vs. 31% in the negative-ion spectrum. FTICR mass spectral data indicated that most of the refractory DON compounds (i.e. nonreactive during the 5 days of the incubation) had molecular compositions representative of lignin-like molecules, while lipid-like and protein-like molecules comprised most of the small reactive component of the DON pool. From these data we conclude that (+) APPI FTICRMS is a promising technique for describing the molecular composition of DON mixtures. The technique is particularly valuable in assessing the bioavailability of individual components of DON when combined with bioassays. Copyright © 2013 John Wiley & Sons, Ltd.

Alkylation of organic aromatic compounds

DOEpatents

Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

1993-09-07

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 figures.

Alkylation of organic aromatic compounds

DOEpatents

Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

1993-01-01

Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

Organic compounds in produced waters from coalbed natural gas wells in the Powder River Basin, Wyoming, USA

USGS Publications Warehouse

Orem, W.H.; Tatu, C.A.; Lerch, H.E.; Rice, C.A.; Bartos, T.T.; Bates, A.L.; Tewalt, S.; Corum, M.D.

2007-01-01

The organic composition of produced water samples from coalbed natural gas (CBNG) wells in the Powder River Basin, WY, sampled in 2001 and 2002 are reported as part of a larger study of the potential health and environmental effects of organic compounds derived from coal. The quality of CBNG produced waters is a potential environmental concern and disposal problem for CBNG producers, and no previous studies of organic compounds in CBNG produced water have been published. Organic compounds identified in the produced water samples included: phenols, biphenyls, N-, O-, and S-containing heterocyclic compounds, polycyclic aromatic hydrocarbons (PAHs), aromatic amines, various non-aromatic compounds, and phthalates. Many of the identified organic compounds (phenols, heterocyclic compounds, PAHs) are probably coal-derived. PAHs represented the group of organic compounds most commonly observed. Concentrations of total PAHs ranged up to 23 ??g/L. Concentrations of individual compounds ranged from about 18 to <0.01 ??g/L. Temporal variability of organic compound concentrations was documented, as two wells with relatively high organic compound contents in produced water in 2001 had much lower concentrations in 2002. In many areas, including the PRB, coal strata provide aquifers for drinking water wells. Organic compounds observed in produced water are also likely present in drinking water supplied from wells in the coal. Some of the organic compounds identified in the produced water samples are potentially toxic, but at the levels measured in these samples are unlikely to have acute health effects. The human health effects of low-level, chronic exposure to coal-derived organic compounds in drinking water are currently unknown. Continuing studies will evaluate possible toxic effects from low level, chronic exposure to coal-derived organic compounds in drinking water supplies.

Effects of organic and conventional cultivation methods on composition of eggplant fruits.

PubMed

Raigón, María D; Rodríguez-Burruezo, Adrián; Prohens, Jaime

2010-06-09

Organic food is associated by the general public with improved nutritional properties, and this has led to increasing demand for organic vegetables. The effects of organic and conventional cultivation methods on dry matter, protein, minerals, and total phenolic content has been studied for two successive years in two landraces and one commercial hybrid of eggplant. In the first year, organically produced eggplants had higher mean contents (expressed on a fresh weight basis) of K (196 vs 171 mg 100 g(-1)), Ca (11.1 vs 8.7 mg 100 g(-1)), Mg (6.0 vs 4.6 mg 100 g(-1)), and total phenolics (49.8 vs 38.2 mg 100 g(-1)) than conventionally grown eggplants. In the second year, in which matched plots having a history of organic management were cultivated following organic or conventional fertilization practices, organically produced eggplants still had higher contents of K (272 vs 249 mg 100 g(-1)) and Mg (8.8 vs 7.6), as well as of Cu (0.079 vs 0.065 mg 100 g(-1)), than conventionally fertilized eggplants. Conventionally cultivated eggplants had a higher polyphenol oxidase activity than organically cultivated ones (3.19 vs 2.17 enzyme activity units), although no differences in browning were observed. Important differences in mineral concentrations between years were detected, which resulted in many correlations among mineral contents being significant. The first component of the principal component analysis separates the eggplants according to year, whereas the second component separates them according to the cultivation method (organic or conventional). Overall, the results show that organic management and fertilization have a positive effect on the accumulation of certain beneficial minerals and phenolic compounds in eggplant and that organically and conventionally produced eggplants might be distinguished according to their composition profiles.

Molecular marker characterization and source appointment of particulate matter and its organic aerosols.

PubMed

Choi, Jong-Kyu; Ban, Soo-Jin; Kim, Yong-Pyo; Kim, Yong-Hee; Yi, Seung-Muk; Zoh, Kyung-Duk

2015-09-01

This study was carried out to identify possible sources and to estimate their contribution to total suspended particle (TSP) organic aerosol (OA) contents. A total of 120 TSP and PM2.5 samples were collected simultaneously every third day over a one-year period in urban area of Incheon, Korea. High concentration in particulate matters (PM) and its components (NO3(-), water soluble organic compounds (WSOCs), and n-alkanoic acids) were observed during the winter season. Among the organics, n-alkanes, n-alkanoic acids, levoglucosan, and phthalates were major components. Positive matrix factorization (PMF) analysis identified seven sources of organic aerosols including combustion 1 (low molecular weight (LMW)-polycyclic aromatic hydrocarbons (PAHs)), combustion 2 (high molecular weight (HMW)-PAHs), biomass burning, vegetative detritus (n-alkane), secondary organic aerosol 1 (SOA1), secondary organic aerosol 2 (SOA2), and motor vehicles. Vegetative detritus increased during the summer season through an increase in biogenic/photochemical activity, while most of the organic sources were prominent in the winter season due to the increases in air pollutant emissions and atmospheric stability. The correlation factors were high among the main components of the organic carbon (OC) in the TSP and PM2.5. The results showed that TSP OAs had very similar characteristics to the PM2.5 OAs. SOA, combustion (PAHs), and motor vehicle were found to be important sources of carbonaceous PM in this region. Our results imply that molecular markers (MMs)-PMF model can provide useful information on the source and characteristics of PM. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sources, composition and absorption Ångström exponent of light-absorbing organic components in aerosol extracts from the Los Angeles Basin.

PubMed

Zhang, Xiaolu; Lin, Ying-Hsuan; Surratt, Jason D; Weber, Rodney J

2013-04-16

We investigate the sources, chemical composition, and spectral properties of light-absorbing organic aerosol extracts (i.e., brown carbon, or BrC) in the Los Angeles (LA) Basin during the CalNex-2010 field campaign. Light absorption of PM2.5 water-soluble components at 365 nm (Abs365), used as a proxy for water-soluble BrC, was well correlated with water-soluble organic carbon (WSOC) (r(2) = 0.55-0.65), indicating secondary organic aerosol (SOA) formation from anthropogenic emissions was the major source of water-soluble BrC in this region. Normalizing Abs365 to WSOC mass yielded an average solution mass absorption efficiency (MAE365) of 0.71 m(2) g(-1) C. Detailed chemical speciation of filter extracts identified eight nitro-aromatic compounds that were correlated with Abs365. These compounds accounted for ∼4% of the overall water-soluble BrC absorption. Methanol-extracted BrC in LA was approximately 3 and 21 times higher than water-soluble BrC at 365 and 532 nm, respectively, and had a MAE365 of 1.58 m(2) g(-1) C (Abs365 normalized to organic carbon mass). The water-insoluble BrC was strongly correlated with ambient elemental carbon concentration, suggesting similar sources. Absorption Ångström exponent (Å(a)) (fitted between 300 and 600 nm wavelengths) was 3.2 (±1.2) for the PILS water-soluble BrC measurement, compared to 4.8 (±0.5) and 7.6 (±0.5) for methanol- and water-soluble BrC from filter extracts, respectively. These results show that fine particle BrC was prevalent in the LA basin during CalNex, yet many of its properties and potential impacts remain unknown.

Wine, resveratrol and health: a review.

PubMed

Guerrero, Raúl F; García-Parrilla, Maria C; Puertas, Belén; Cantos-Villar, Emma

2009-05-01

Several studies have cited the Mediterranean diet as an example of healthy eating. In fact, the Mediterranean diet has become the reference diet for the prevention of cardiovascular disease. Red wine seems to be an essential component of the diet, since moderate consumption of wine is associated with lower risk and mortality from cardiovascular disease. Evidence is also accumulating that wine helps prevent the development of certain cancers. Of all the many components of wine, resveratrol, which is a natural component specifically present in wine, has been identified as being mainly responsible for these health-promoting properties. Many valuable properties such as cardioprotective and anticarcinogenic activity have been attributed to resveratrol; however, its bioavailability is quite low. The bioactivity of metabolites derived from resveratrol, and the accumulation of resveratrol in vital organs are still under study, but there are high expectations of positive results. Other stilbene compounds are also considered in this review, despite being present in undetectable or very small quantities in wine. The present paper reviews all aspects of the health properties of wine, bioactive compounds found in wine, and their concentrations, bioavailability and possible synergistic effects.

Preliminary characterization of submicron secondary aerosol in the amazon forest - ATTO station

NASA Astrophysics Data System (ADS)

Carbone, S.; Ferreira De Brito, J.; Andreae, M. O.; Pöhlker, C.; Chi, X.; Saturno, J.; Barbosa, H. M.; Artaxo, P.

2014-12-01

Biogenic secondary organic aerosol particles are investigated in the Amazon in the context of the GoAmazon Project. The forest naturally emits a large number of gaseous compounds; they are called the volatile organic compounds (VOCs). They are emitted through processes that are not totally understood. Part of those gaseous compounds are converted into aerosol particles, which affect the biogeochemical cycles, the radiation balance, the mechanisms involving cloud formation and evolution, among few other important effects. In this study the aerosol life-cycle is investigated at the ATTO station, which is located about 150 km northeast of Manaus, with emphasis on the natural organic component and its impacts in the ecosystem. To achieve these objectives physical and chemical aerosol properties have been investigated, such as the chemical composition with aerosol chemical speciation monitor (ACSM), nanoparticle size distribution (using the SMPS - Scanning Mobility Particle Sizer), optical properties with measurements of scattering and absorption (using nephelometers and aethalometers). Those instruments have been operating continuously since February 2014 together with trace gases (O3, CO2, CO, SO2 and NOx) analyzers and additional meteorological instruments. On average PM1 (the sum of black carbon, organic and inorganic ions) totalized 1.0±0.3 μg m-3, where the organic fraction was dominant (75%). During the beginning of the dry season (July/August) the organic aerosol presented a moderate oxygenated character with the oxygen to carbon ratio (O:C) of 0.7. In the wet season some episodes containing significant amount of chloride and backward wind trajectories suggest aerosol contribution from the Atlantic Ocean. A more comprehensive analysis will include an investigation of the different oxidized fractions of the organic aerosol and optical properties.

Conversion of sulfur compounds and microbial community in anaerobic treatment of fish and pork waste.

PubMed

He, Ruo; Yao, Xing-Zhi; Chen, Min; Ma, Ruo-Chan; Li, Hua-Jun; Wang, Chen; Ding, Shen-Hua

2018-06-01

Volatile sulfur compounds (VSCs) are not only the main source of malodor in anaerobic treatment of organic waste, but also pose a threat to human health. In this study, VSCs production and microbial community was investigated during the anaerobic degradation of fish and pork waste. The results showed that after the operation of 245 days, 94.5% and 76.2% of sulfur compounds in the fish and pork waste was converted into VSCs. Among the detected VSCs including H 2 S, carbon disulfide, methanethiol, ethanethiol, dimethyl sulfide, dimethyl disulfide and dimethyl trisulfide, methanethiol was the major component with the maximum concentration of 4.54% and 3.28% in the fish and pork waste, respectively. The conversion of sulfur compounds including total sulfur, SO 4 2- -S, S 2- , methionine and cysteine followed the first-order kinetics. Miseq sequencing analysis showed that Acinetobacter, Clostridium, Proteus, Thiobacillus, Hyphomicrobium and Pseudomonas were the main known sulfur-metabolizing microorganisms in the fish and pork waste. The C/N value had most significant influence on the microbial community in the fish and pork waste. A main conversion of sulfur compounds with CH 3 SH as the key intermediate was firstly hypothesized during the anaerobic degradation of fish and pork waste. These findings are helpful to understand the conversion of sulfur compounds and to develop techniques to control ordor pollution in the anaerobic treatment of organic waste. Copyright © 2018 Elsevier Ltd. All rights reserved.

Contribution of microorganisms to non-extractable residue formation during biodegradation of ibuprofen in soil.

PubMed

Nowak, Karolina M; Girardi, Cristobal; Miltner, Anja; Gehre, Matthias; Schäffer, Andreas; Kästner, Matthias

2013-02-15

Non-extractable residues (NER) formed during biodegradation of organic contaminants in soil are considered to be mainly composed of parent compounds or their primary metabolites with hazardous potential. However, in the case of biodegradable organic compounds, the soil NER may also contain microbial biomass components, for example fatty acids (FA) and amino acids (AA). After cell death, these biomolecules are subsequently incorporated into non-living soil organic matter (SOM) and are stabilised ultimately forming hardly extractable residues of biogenic origin. We investigated biodegradation of (13)C(6)-ibuprofen, in particular the metabolic incorporation of the (13)C-label into FA and AA and their fate in soil over 90 days. (13)C-FA and (13)C-AA amounts in the living microbial biomass fraction initially increased, then decreased over time and were continuously incorporated into the non-living SOM pool. The (13)C-FA in the non-living SOM remained stable from day 59 whereas the contents of (13)C-AA slightly increased until the end. After 90 days, nearly all NER were biogenic as they were made up almost completely by natural biomass compounds. The presented data demonstrated that the potential environmental risks related to the ibuprofen-derived NER are overestimated. Copyright © 2012 Elsevier B.V. All rights reserved.

Alchemical and structural distribution based representation for universal quantum machine learning

NASA Astrophysics Data System (ADS)

Faber, Felix A.; Christensen, Anders S.; Huang, Bing; von Lilienfeld, O. Anatole

2018-06-01

We introduce a representation of any atom in any chemical environment for the automatized generation of universal kernel ridge regression-based quantum machine learning (QML) models of electronic properties, trained throughout chemical compound space. The representation is based on Gaussian distribution functions, scaled by power laws and explicitly accounting for structural as well as elemental degrees of freedom. The elemental components help us to lower the QML model's learning curve, and, through interpolation across the periodic table, even enable "alchemical extrapolation" to covalent bonding between elements not part of training. This point is demonstrated for the prediction of covalent binding in single, double, and triple bonds among main-group elements as well as for atomization energies in organic molecules. We present numerical evidence that resulting QML energy models, after training on a few thousand random training instances, reach chemical accuracy for out-of-sample compounds. Compound datasets studied include thousands of structurally and compositionally diverse organic molecules, non-covalently bonded protein side-chains, (H2O)40-clusters, and crystalline solids. Learning curves for QML models also indicate competitive predictive power for various other electronic ground state properties of organic molecules, calculated with hybrid density functional theory, including polarizability, heat-capacity, HOMO-LUMO eigenvalues and gap, zero point vibrational energy, dipole moment, and highest vibrational fundamental frequency.

Assessment of semi-volatile organic compounds in drinking water sources in Jiangsu, China.

PubMed

Wu, Yifeng; Jia, Yongzhi; Lu, Xiwu

2013-08-01

Many xenobiotic compounds, especially organic pollutants in drinking water, can cause threats to human health and natural ecosystems. The ability to predict the level of pollutants and identify their source is crucial for the design of pollutant risk reduction plans. In this study, 25 semi-volatile organic compounds (SVOCs) were assessed at 16 monitoring sites of drinking water sources in Jiangsu, east China, to evaluate water quality conditions and source of pollutants. Four multivariate statistical techniques were used for this analysis. The correlation test indicated that 25 SVOCs parameters variables had a significant spatial variability (P<0.05). The results of correlation analysis, principal component analysis (PCA) and cluster analysis (CA) suggested that at least four sources, i.e., agricultural residual pesticides, industrial sewage, water transportation vehicles and miscellaneous sources, were responsible for the presence of SVOCs in the drinking water sites examined, accounting for 89.6% of the total variance in the dataset. The analysis of site similarity showed that 16 sites could be divided into high, moderate, and low pollutant level groups at (D(link)/D(max))×25<10, and each group had primary typical SVOCs. These results provide useful information for developing appropriate strategies for contaminants control in drinking water sources. Copyright © 2013 Elsevier Inc. All rights reserved.

Insights into the sorption properties of cutin and cutan biopolymers.

PubMed

Shechter, Michal; Chefetz, Benny

2008-02-15

Plant cuticles have been reported as highly efficient sorbents for organic compounds. The objective of this study was to elucidate the sorption and desorption behavior of polar and nonpolar organic compounds with the major structural components of the plant cuticle: the biopolymers cutin and cutan. The sorption affinity values of the studied compounds followed the order: phenanthrene > atrazine > chlorotoluron > carbamazepine. A higher sorption affinity of phenanthrene and atrazine to cutin was probably due to the higher level of amorphous paraffinic carbon in this biopolymer. Phenanthrene exhibited reversible sorption behavior and a high ratio of organic-carbon-normalized distribution coefficient (Koc) to carbon-normalized octanol-water partitioning coefficients (Kowc) with both biopolymers. This suggests that both biopolymers provide phenanthrene with a partition medium for hydrophobic interactions with the flexible long alkyl-chain moieties of the biopolymers. The low Koc/Kowc ratios obtained for the polar sorbates suggest that the polar sites in the biopolymers are not accessible for sorption interactions. Atrazine and carbamazepine exhibited sorption-desorption hysteresis with both sorbents, indicating that both sorbates interact with cutin and cutan via both hydrophobic and specific interactions. In general, the sorptive properties of the studied biopolymers were similar, signifying that the active sorption sites are similar even though the biopolymers exhibit different properties.

Quadruple sulfur isotope constraints on the origin and cycling of volatile organic sulfur compounds in a stratified sulfidic lake

NASA Astrophysics Data System (ADS)

Oduro, Harry; Kamyshny, Alexey; Zerkle, Aubrey L.; Li, Yue; Farquhar, James

2013-11-01

We have quantified the major forms of volatile organic sulfur compounds (VOSCs) distributed in the water column of stratified freshwater Fayetteville Green Lake (FGL), to evaluate the biogeochemical pathways involved in their production. The lake's anoxic deep waters contain high concentrations of sulfate (12-16 mmol L-1) and sulfide (0.12 μmol L-1 to 1.5 mmol L-1) with relatively low VOSC concentrations, ranging from 0.1 nmol L-1 to 2.8 μmol L-1. Sulfur isotope measurements of combined volatile organic sulfur compounds demonstrate that VOSC species are formed primarily from reduced sulfur (H2S/HS-) and zero-valent sulfur (ZVS), with little input from sulfate. Thedata support a role of a combination of biological and abiotic processes in formation of carbon-sulfur bonds between reactive sulfur species and methyl groups of lignin components. These processes are responsible for very fast turnover of VOSC species, maintaining their low levels in FGL. No dimethylsulfoniopropionate (DMSP) was detected by Electrospray Ionization Mass Spectrometry (ESI-MS) in the lake water column or in planktonic extracts. These observations indicate a pathway distinct from oceanic and coastal marine environments, where dimethylsulfide (DMS) and other VOSC species are principally produced via the breakdown of DMSP by plankton species.

Composition of the black crusts from the Saint Denis Basilica, France, as revealed by gas chromatography-mass spectrometry.

PubMed

Gaviño, Maria; Hermosin, Bernardo; Vergès-Belmin, Véronique; Nowik, Witold; Saiz-Jimenez, Cesareo

2004-05-01

The organic fraction of black crusts from Saint Denis Basilica, France, is composed of a complex mixture of aliphatic and aromatic compounds. These compounds were studied by two different analytical approaches: tetramethyl ammonium hydroxide (TMAH) thermochemolysis in combination with gas chromatography-mass spectrometry (GC-MS), and solvent extraction, fractionation by silica column, and identification of the fraction components by GC-MS. The first approach, feasible at the microscale level, is able to supply fairly general information on a wide range of compounds. Using the second approach, we were able to separate the complex mixture of compounds into four fractions, enabling a better identification of the extractable compounds. These compounds belong to different classes: aliphatic hydrocarbons (nalkanes, n-alkenes), aliphatic and aromatic carboxylic acids (n-fatty acids, alpha,omega-dicarboxylic acids, and benzenecarboxylic acids), polycyclic aromatic hydrocarbons (PAH), and molecular biomarkers (isoprenoid hydrocarbons, diterpenoids, and triterpenoids). With each approach, similar classes of compounds were identified, although TMAH thermochemolysis failed to identify compounds present at low concentrations in black crusts. The two proposed methodological approaches are complementary, particularly in the study of polar fractions.

ACID EVAPORATION OF ULTIMA GOLD TM AB LIQUID SCINTILLATION COCKTAIL RESIDUE

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

Kyser, E.; Fondeur, F.; Crump, S.

2011-12-21

Prior analyses of samples from the F/H Lab solutions showed the presence of diisopropylnapthalene (DIN), a major component of Ultima Gold{trademark} AB liquid scintillation cocktail (LSC). These solutions are processed through H-Canyon Tank 10.5 and ultimately through the 17.8E evaporator. Similar solutions originated in SRNL streams sent to the same H Canyon tanks. This study examined whether the presence of these organics poses a process-significant hazard for the evaporator. Evaporation and calorimetry testing of surrogate samples containing 2000 ppm of Ultima Gold{trademark} AB LSC in 8 M nitric acid have been completed. These experiments showed that although reactions between nitricmore » acid and the organic components do occur, they do not appear to pose a significant hazard for runaway reactions or generation of energetic compounds in canyon evaporators. The amount of off-gas generated was relatively modest and appeared to be well within the venting capacity of the H-Canyon evaporators. A significant fraction of the organic components likely survives the evaporation process primarily as non-volatile components that are not expected to represent any new process concerns during downstream operations such as neutralization. Laboratory Waste solutions containing minor amounts of DIN can be safely received, stored, transferred, and processed through the canyon waste evaporator.« less

DETAILED ANALYSIS OF SOA ORIGINATING FROM THE PHOTOOXIDATION OF D-LIMONENE IN THE PRESENCE OF NO X AND UV LIGHT AND ITS IMPLICATION TO AMBIENT PM 2.5

EPA Science Inventory

A detailed analysis was carried out of the aerosol phase originated from the photooxidation of d-limonene in the presence of NO_x and artificial light with the analytical emphasis on the identification of oxygenated organic compounds. The major components included six ...

Carbon Dioxide Corrosion and Acetate: A Hypothesis on the Influence of Microorganisms

DTIC Science & Technology

2008-11-01

thermocatalytic degradation of kero- gen,5 oxidation of suitable acid precursors," "and the pyrolytic destruction of kerogen or oil components.*IS... oil industry. Both chemical compounds can be produced and consumed by microorganisms during the anaerobic biodegradation of organic matter- including...hydrocarbons. We contend that the principles governing anaerobic biodegration activity can be extrapolated to above ground oil production facilities

Dormancy and Recovery Testing for Biological Wastewater Processors

NASA Technical Reports Server (NTRS)

Hummerick, Mary F.; Coutts, Janelle L.; Lunn, Griffin M.; Spencer, LaShelle; Khodadad, Christina L.; Birmele, Michele N.; Frances, Someliz; Wheeler, Raymond

2015-01-01

Resource recovery and recycling waste streams to usable water via biological water processors is a plausible component of an integrated water purification system. Biological processing as a pretreatment can reduce the load of organic carbon and nitrogen compounds entering physiochemical systems downstream. Aerated hollow fiber membrane bioreactors, have been proposed and studied for a number of years as an approach for treating wastewater streams for space exploration.

Antiknock evaluation of hydrocarbons and ethers as aviation fuel components

NASA Technical Reports Server (NTRS)

Barnett, Henry C

1950-01-01

The results of a NACA investigation conducted over a period of several years to evaluate the anti-knock characteristics of organic compounds are summarized. Included are data for 18 branched paraffins and olefins, 27 aromatics, and 22 ethers. The factors of performance investigated were blending characteristics, temperature sensitivity, lead response, and relation between molecular structure and antiknock ratings. Four engines were used.

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

Shah, Kedar G.; Pannu, Satinderpall S.

An integrated circuit system having an integrated circuit (IC) component which is able to have its functionality destroyed upon receiving a command signal. The system may involve a substrate with the IC component being supported on the substrate. A module may be disposed in proximity to the IC component. The module may have a cavity and a dissolving compound in a solid form disposed in the cavity. A heater component may be configured to heat the dissolving compound to a point of sublimation where the dissolving compound changes from a solid to a gaseous dissolving compound. A triggering mechanism maymore » be used for initiating a dissolution process whereby the gaseous dissolving compound is allowed to attack the IC component and destroy a functionality of the IC component.« less

Extractable organic matter in PM10 from LiWan district of Guangzhou City, PR China.

PubMed

Bi, Xinhui; Sheng, Guoying; Peng, Peng an; Zhang, Zhiqiang; Fu, Jiamo

2002-12-02

PM10 (particulate matter with aerodynamic diameter <10 microm) samples were collected at LiWan District of Guangzhou, PR China during April and July 2001 using a high volume air sampler to determine the distributions of homologous compounds and biomarkers. Polycyclic aromatic hydrocarbons (PAHs) including non-alkylated PAHs, methyl-alkylated PAHs, and some PAHs containing S/O atoms and n-alkanes were measured using gas chromatography/mass spectrometry analysis. The sigma(n)-alkane and sigmaPAHs ranged from 26.4 to 719.2 ng/m3 and 7.4 to 159.4 ng/m3, respectively. A seasonal fluctuation was clearly evident with higher concentrations occurring during the colder months (April). In addition, some compositional differences are observed for the organic compounds in samples collected from different heights above ground level. Higher sites had a significant contribution from vascular plant wax. The presence of petroleum products with no carbon number preference, pristane, phytane and a significant unresolved complex mixture (UCM) with unresolved to resolved components ratio (U/R) of 6.2-13.2 confirm the petroleum component. The relative distribution of n-alkanes and the values of molecular diagnostic ratio, such as carbon preference index (CPI) values ranging from 1.0 to 1.4 (for the whole range of n-alkanes), indicated the importance of petroleum and diesel residues and gasoline emissions, as well as the minor contribution of n-alkanes emitted directly from epicuticular waxes. Indeed, the percent contribution of leaf 'wax' n-alkanes (5.2-19.4%) indicated a low contribution of biogenic sources. The fossil fuel biomarkers, hopanes and steranes were observed in the PM10 samples, which indicate a petroleum origin. The distribution pattern of PAHs was characteristic of anthropogenic emissions. Coupling carbon number maximum (Cmax), CPI, U/R values, molecular marker and molecular diagnostic ratios for alkanes and PAHs revealed a classification of natural biogenic and anthropogenic components of atmospheric aerosols. These analyses support the conclusion that vehicular emission was the major source of organic compounds during the study period, while the contribution of epicuticular waxes emitted by terrestrial plants was minor.

Volatile, isotope, and organic analysis of martian fines with the Mars Curiosity rover.

PubMed

Leshin, L A; Mahaffy, P R; Webster, C R; Cabane, M; Coll, P; Conrad, P G; Archer, P D; Atreya, S K; Brunner, A E; Buch, A; Eigenbrode, J L; Flesch, G J; Franz, H B; Freissinet, C; Glavin, D P; McAdam, A C; Miller, K E; Ming, D W; Morris, R V; Navarro-González, R; Niles, P B; Owen, T; Pepin, R O; Squyres, S; Steele, A; Stern, J C; Summons, R E; Sumner, D Y; Sutter, B; Szopa, C; Teinturier, S; Trainer, M G; Wray, J J; Grotzinger, J P

2013-09-27

Samples from the Rocknest aeolian deposit were heated to ~835°C under helium flow and evolved gases analyzed by Curiosity's Sample Analysis at Mars instrument suite. H2O, SO2, CO2, and O2 were the major gases released. Water abundance (1.5 to 3 weight percent) and release temperature suggest that H2O is bound within an amorphous component of the sample. Decomposition of fine-grained Fe or Mg carbonate is the likely source of much of the evolved CO2. Evolved O2 is coincident with the release of Cl, suggesting that oxygen is produced from thermal decomposition of an oxychloride compound. Elevated δD values are consistent with recent atmospheric exchange. Carbon isotopes indicate multiple carbon sources in the fines. Several simple organic compounds were detected, but they are not definitively martian in origin.

Computational and experimental study of the interactions between ionic liquids and volatile organic compounds.

PubMed

Gao, Tingting; Andino, Jean M; Alvarez-Idaboy, J Raul

2010-09-07

Computational chemistry calculations were performed to investigate the interactions of ionic liquids with different classes of volatile organic compounds (VOCs), including alcohols, aldehydes, ketones, alkanes, alkenes, alkynes and aromatic compounds. At least one VOC was studied to represent each class. Initially, 1-butyl-3-methylimindazolium chloride (abbreviated as C(4)mimCl) was used as the test ionic liquid compound. Calculated interaction lengths between atoms in the ionic liquid and the VOC tested as well as thermodynamic data suggest that C(4)mimCl preferentially interacts with alcohols as compared to other classes of volatile organic compounds. The interactions of methanol with different kinds of ionic liquids, specifically 1-butyl-3-methylimidazolium bromine (C(4)mimBr) and 1-butyl-3-methylimidazolium tetrafluoroborate (C(4)mimBF(4)) were also studied. In comparing C(4)mimCl, C(4)mimBr, and C(4)mimBF(4), the computational results suggest that C(4)mimCl is more likely to interact with methanol. Laboratory experiments were performed to provide further evidence for the interaction between C(4)mimCl and different classes of VOCs. Fourier transform infrared spectroscopy was used to probe the ionic liquid surface before and after exposure to the VOCs that were tested. New spectral features were detected after exposure of C(4)mimCl to various alcohols. The new features are characteristic of the alcohols tested. No new IR features were detected after exposure of the C(4)mimCl to the aldehyde, ketone, alkane, alkene, alkyne or aromatic compounds studied. In addition, after exposing the C(4)mimCl to a multi-component mixture of various classes of compounds (including an alcohol), the only new peaks that were detected were characteristic of the alcohol that was tested. These experimental results demonstrated that C(4)mimCl is selective to alcohols, even in complex mixtures. The findings in this work provide information for future gas-phase alcohol sensor design.

Emission pattern of semi-volatile organic compounds from recycled styrenic polymers using headspace solid-phase microextraction gas chromatography-mass spectrometry.

PubMed

Vilaplana, Francisco; Martínez-Sanz, Marta; Ribes-Greus, Amparo; Karlsson, Sigbritt

2010-01-15

The emission of low molecular weight compounds from recycled high-impact polystyrene (HIPS) has been investigated using headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS). Four released target analytes (styrene, benzaldehyde, acetophenone, and 2-phenylpropanal) were selected for the optimisation of the HS-SPME sampling procedure, by analysing operating parameters such as type of SPME fibre (polarity and operating mechanism), particle size, extraction temperature and time. 26 different compounds were identified to be released at different temperatures from recycled HIPS, including residues of polymerisation, oxidated derivates of styrene, and additives. The type of SPME fibre employed in the sampling procedure affected the detection of emitted components. An adsorptive fibre such as carbowax/polydimethylsiloxane (CAR/PDMS fibre) offered good selectivity for both non-polar and polar volatile compounds at lower temperatures; higher temperatures result in interferences from less-volatile released compounds. An absorptive fibre as polydimethylsiloxane (PDMS) fibre is suitable for the detection of less-volatile non-polar molecules at higher temperatures. The nature and relative amount of the emitted compounds increased with higher exposure temperature and smaller polymeric particle size. HS-SPME proves to be a suitable technique for screening the emission of semi-volatile organic compounds (SVOCs) from polymeric materials; reliable quantification of the content of target analytes in recycled HIPS is however difficult due to the complex mass-transfer processes involved, matrix effects, and the difficulties in equilibrating the analytical system. 2009 Elsevier B.V. All rights reserved.

LIQUID PHASE SINTERING OF METALLIC CARBIDES

DOEpatents

Hammond, J.; Sease, J.D.

1964-01-21

An improved method is given for fabricating uranium carbide composites, The method comprises forming a homogeneous mixture of powdered uranium carbide, a uranium intermetallic compound which wets and forms a eutectic with said carbide and has a non-uranium component which has a relatively high vapor pressure at a temperature in the range 1200 to 1500 deg C, and an organic binder, pressing said mixture to a composite of desired green strength, and then vacuum sintering said composite at the eutectic forming temperature for a period sufficient to remove at least a portion of the non-uranium containing component of said eutectic. (AEC)

Organic matter in primitive meteorites: a study of the hydrogen isotopic distribution in CM-type carbonaceous chondrites

NASA Astrophysics Data System (ADS)

Piani, L.; Yurimoto, H.; Remusat, L.; Gonzales, A.; Marty, B.

2017-12-01

Chondrite meteorites are fragments of rocks coming from small bodies of the asteroid belt and constitute witnesses of the volatile-rich reservoirs present in the inner protoplanetary disk. Among these meteorites, carbonaceous chondrites contain the largest quantity of water and organic matter and are one of the most probable candidates for the delivery of water and molecular origin of life to Earth. Organic matter in carbonaceous chondrites is intimately mixed with hydrated minerals challenging its in situ characterization and the determination of its H-isotope composition (Le Guillou et al., GCA 131, 2014). Organic matter occurs as soluble components (in water or organic solvents) and an insoluble macromolecule. The insoluble organic matter (IOM) is efficiently isolated after acid leaching of the chondrite minerals. IOM has thus been investigated by a large set of analytical techniques allowing its structural organization, chemical composition and isotopic composition to be determined at several scales (e.g. Derenne and Robert, MAPS 45, 2010). In the soluble counterpart (SOM), targeted studies have shown large ranges of D/H ratios in the different classes of soluble organic compounds (i.e. carboxylic acids, ketones and aldehydes, amino-acids etc.) (Remusat, Planetary Mineralogy 15, 2015 and references therein). This D/H distribution indicates a complex and probably multiple-stage synthesis of this organic compounds occurring at different stages of the disk evolution. Nevertheless, inventories of the known C-bearing species in carbonaceous chondrites (carbonates, SOM and IOM) show that about 40-50 % of the carbon is hidden within the matrix (Alexander et al., MAPS 50, 2015). In this study, we perform in situ hydrogen isotope analyses at the micrometer scale by secondary ion mass spectrometry to investigate the distribution of organic matter in primitive chondrites without the use of any chemical treatment. Correlated analyses of the D/H and C/H ratios allow us to decipher the H contribution of water-bearing minerals and to estimate the hydrogen isotopic composition of water in chondrites (Piani et al., submitted). Comparison of spot analyses and isotope images obtained in situ and on isolated IOM gives clues on the nature of the organic components of carbonaceous asteroid rocks.

Contribution of inorganic and organic components to sorption of neutral and ionizable pharmaceuticals by sediment/soil.

PubMed

Yamamoto, Hiroshi; Takemoto, Kohei; Tamura, Ikumi; Shin-Oka, Norihiro; Nakano, Takahiro; Nishida, Masayo; Honda, Yuta; Moriguchi, Shigemi; Nakamura, Yudai

2018-03-01

Our previous study showed that the sorption coefficient of certain polar pharmaceuticals to river sediment, especially particular amines, was unexpectedly high. Thus, we conducted sorption experiments of selected polar pharmaceuticals and pyrene derivatives, including amines, carboxylic acids, and neutral compounds, to model clay minerals, i.e., montmorillonite and kaolin, in addition to silica sands and humic substances. The contribution of each component was roughly estimated by simple fractionation of the individual sorption coefficients. Relatively high sorption coefficients (K d values) were found, especially for amines on clay minerals, which suggest that electrochemical affinity may play an important role. The estimated contribution percentage suggests a relatively large contribution from inorganic constituents, such as clay minerals, for silt loam soil; in contrast, organic components predominantly contribute for sandy river sediments. These findings could be the key to understanding not only the fate and transport but also bioavailability and environmental risks of pharmaceuticals, which are mostly polar and/or ionizable.

Supercritical Fluid Extraction and Analysis of Tropospheric Aerosol Particles

NASA Astrophysics Data System (ADS)

Hansen, Kristen J.

An integrated sampling and supercritical fluid extraction (SFE) cell has been designed for whole-sample analysis of organic compounds on tropospheric aerosol particles. The low-volume extraction cell has been interfaced with a sampling manifold for aerosol particle collection in the field. After sample collection, the entire SFE cell was coupled to a gas chromatograph; after on-line extraction, the cryogenically -focused sample was separated and the volatile compounds detected with either a mass spectrometer or a flame ionization detector. A 20-minute extraction at 450 atm and 90 ^circC with pure supercritical CO _2 is sufficient for quantitative extraction of most volatile compounds in aerosol particle samples. A comparison between SFE and thermal desorption, the traditional whole-sample technique for analyses of this type, was performed using ambient aerosol particle samples, as well as samples containing known amounts of standard analytes. The results of these studies indicate that SFE of atmospheric aerosol particles provides quantitative measurement of several classes of organic compounds. SFE provides information that is complementary to that gained by the thermal desorption analysis. The results also indicate that SFE with CO _2 can be validated as an alternative to thermal desorption for quantitative recovery of several organic compounds. In 1989, the organic constituents of atmospheric aerosol particles collected at Niwot Ridge, Colorado, along with various physical and meteorological data, were measured during a collaborative field study. Temporal changes in the composition of samples collected during summertime at the rural site were studied. Thermal desorption-GC/FID was used to quantify selected compounds in samples collected during the field study. The statistical analysis of the 1989 Niwot Ridge data set is presented in this work. Principal component analysis was performed on thirty-one variables selected from the data set in order to ascertain different source and process components, and to examine concentration changes in groups of variables with respect to time of day and meteorological conditions. Seven orthogonal groups of variables resulted from the statistical analysis; the groups serve as molecular markers for different biologic and anthropogenic emission sources. In addition, the results of the statistical analysis were used to investigate how several emission source contributions vary with respect to local atmospheric dynamics. Field studies were conducted in the urban environment in and around Boulder, CO. to characterize the dynamics, chemistry, and emission sources which affect the composition and concentration of different size-fractions of aerosol particles in the Boulder air mass. Relationships between different size fractions of particles and some gas-phase pollutants were elucidated. These field studies included an investigation of seasonal variations in the organic content and concentration of aerosol particles, and how these characteristics are related to local meteorology and to the concentration of some gas-phase pollutants. The elemental and organic composition of aerosol particles was investigated according to particle size in preliminary studies of size-differentiated samples of aerosol particles. In order to aid in future studies of urban aerosol particles, samples were collected at a forest fire near Boulder. Molecular markers specific to wood burning processes will be useful indicators of residential wood burning activities in future field studies.

Effect of on-site wastewater disposal on quality of ground water and base flow: A pilot study in Chester County, Southeastern Pennsylvania, 2005

USGS Publications Warehouse

Senior, Lisa A.; Cinotto, Peter J.

2007-01-01

On-site wastewater disposal has the potential to introduce contaminants into ground water and subsequently, by ground-water discharge, to streams. A pilot study was conducted during 2005 by the U.S. Geological Survey in cooperation with the Chester County Health Department and the Chester County Water Resources Authority to determine if wastewater components, including inorganic constituents and selected organic wastewater compounds, such as detergents, considered to be emerging contaminants, were present in ground water and stream base flow in areas with on-site wastewater disposal. The study area was a small watershed (about 7.1 square miles) of mixed land use drained by Broad Run in central Chester County, Pa. The area is underlain by fractured metamorphic rocks that form aquifers recharged by precipitation. Surface- and ground-water sampling was done in areas with and without on-site wastewater disposal for comparison, including a relatively densely populated village with cesspools and septic systems, a residential area with septic systems, a residential area served by sewers, and agricultural land. Samples were collected in May-June and September 2005 from eight headwater stream sites under base-flow conditions and in June 2005 from eight wells and two springs. Samples were analyzed for major ions, nutrients, boron, bacteria, and a suite of organic wastewater compounds. Several emerging contaminant wastewater compounds, including detergent components, insect repellents, and flame retardants, were detected in base-flow and ground-water samples. Stream base-flow samples generally contained more compounds and higher concentrations of those compounds than did ground-water samples, and of the ground-water samples, samples from springs contained more compounds and higher concentrations than samples from wells. Concentrations of nitrate, chloride, and boron (inorganic constituents associated with wastewater) generally were all elevated in base-flow and ground-water samples in areas with relatively high densities of on-site wastewater disposal (septic systems or cesspools) compared to other areas sampled. Results of this pilot study should be considered preliminary because of limited data.

Use of fluorescence EEM to monitor the removal of emerging contaminants in full scale wastewater treatment plants.

PubMed

Sgroi, Massimiliano; Roccaro, Paolo; Korshin, Gregory V; Greco, Valentina; Sciuto, Sebastiano; Anumol, Tarun; Snyder, Shane A; Vagliasindi, Federico G A

2017-02-05

This study investigated the applicability of different techniques for fluorescence excitation/emission matrices data interpretations, including peak-picking method, fluorescence regional integration and PARAFAC modelling, to act as surrogates in predicting emerging trace organic compounds (ETOrCs) removal during conventional wastewater treatments that usually comprise primary and secondary treatments. Results showed that fluorescence indexes developed using alternative methodologies but indicative of a same dissolved organic matter component resulted in similar predictions of the removal of the target compounds. The peak index defined by the excitation/emission wavelength positions (λ ex/ λ em ) 225/290nm and related to aromatic proteins and tyrosine-like fluorescence was determined to be a particularly suitable surrogate for monitoring ETOrCs that had very high removal rates (average removal >70%) (i.e., triclosan, caffeine and ibuprofen). The peak index defined by λ ex/ λ em =245/440nm and the PARAFAC component with wavelength of the maxima λ ex/ λ em =245, 350/450, both identified as humic-like fluorescence, were found remarkably well correlated with ETOrCs such as atenolol, naproxen and gemfibrozil that were moderately removed (51-70% average removal). Finally, the PARAFAC component with wavelength of the maxima λ ex/ λ em =<240, 315/380 identified as microbial humic-like fluorescence was the only index correlated with the removal of the antibiotic trimethoprim (average removal 68%). Copyright © 2016 Elsevier B.V. All rights reserved.

The electronic nose as a rapid sensor for volatile compounds in treated domestic wastewater.

PubMed

Dewettinck, T; Van Hege, K; Verstraete, W

2001-07-01

An electronic nose consisting of 12 metal oxide sensors was used to monitor volatile compounds in effluent of a domestic wastewater treatment plant. Effluent and reference (deionized water) samples were heated to 60 and 90 degrees C to promote the volatilization and to increase the sensitivity. An effluent measuring campaign of 12 weeks was conducted and the repeatability and reproducibility of the procedure and the apparatus were determined. Processing the obtained fingerprints with principal component analysis (PCA) allowed interpretation and differentiation of the samples in terms of origin and quality, relative to the reference. To minimize the variance due to sensitivity fluctuations of the apparatus and to detect effluents with deviating qualities, two new concepts were defined, i.e. the relative sensorial odour perception (in short: rSOP) and the relative fingerprint. Correlations between the relative overall electronic nose output, expressed as rSOP, and selected routine parameters were weak except for the parameter "volatile suspended solids" (VSS), indicating adsorption of volatile organic compounds (VOCs) onto the organic particles. The results clearly demonstrate the possibility to use the electronic nose as a rapid alarm generator towards volatile compounds, e.g. in specific advanced treatment processes to produce reclaimed water from effluent of the domestic wastewater treatment plant under scrutiny.

The Biological Diversity and Production of Volatile Organic Compounds by Stem-Inhabiting Endophytic Fungi of Ecuador

PubMed Central

Rundell, Susan M.; Spakowicz, Daniel J.; Narváez-Trujillo, Alexandra; Strobel, Scott A.

2015-01-01

Fungal endophytes colonize every major lineage of land plants without causing apparent harm to their hosts. Despite their production of interesting and potentially novel compounds, endophytes—particularly those inhabiting stem tissues—are still a vastly underexplored component of microbial diversity. In this study, we explored the diversity of over 1500 fungal endophyte isolates collected from three Ecuadorian ecosystems: lowland tropical forest, cloud forest, and coastal dry forest. We sought to determine whether Ecuador’s fungal endophytes are hyperdiverse, and whether that biological diversity is reflected in the endophytes’ chemical diversity. To assess this chemical diversity, we analyzed a subset of isolates for their production of volatile organic compounds (VOCs), a representative class of natural products. This study yielded a total of 1526 fungal ITS sequences comprising some 315 operational taxonomic units (OTUs), resulting in a non-asymptotic OTU accumulation curve and characterized by a Fisher’s α of 120 and a Shannon Diversity score of 7.56. These figures suggest that the Ecuadorian endophytes are hyperdiverse. Furthermore, the 113 isolates screened for VOCs produced more than 140 unique compounds. These results present a mere snapshot of the remarkable biological and chemical diversity of stem-inhabiting endophytic fungi from a single neotropical country. PMID:29376917

The study of volatile organic compounds in urban and indoor air

NASA Astrophysics Data System (ADS)

Clarkson, Paul Jonathan

Chapter 1 is a review of the literature concerning the study of volatile organic compounds in the atmosphere. It examines the basic chemistry of the atmosphere and the roles that organic compounds play in it. Also investigated are the methods of sampling and analysing the volatile organic compounds in the air, paying particular attention to the role of solid phase sampling. Chapter 1 also examines the role of volatile organic compounds on air quality. Chapter 2 describes the experimental procedures that were employed during the course of this research project. Chapter 3 examines a multi-method approach to the study of volatile organic compounds in urban and indoor air. The methods employed were capillary electrophoresis, high performance liquid chromatography and gas chromatography. Although good results were obtained for the various methods that were investigated Chapter 3 concludes that a more unified analytical approach is needed to the study of the air. Chapter 4 investigates the possibilities of using a unified approach to the study of VOC's. This is achieved by the development of an air sampling method that uses solid phase extraction cartridges. By investigating many aspects of air sampling mechanisms the results show that a simple yet efficient method for the sampling of VOC in air has been developed. The SPE method is a reusable, yet reliable method that by using sequential solvent desorption has been shown to exhibit some degree of selectivity. The solid phase that gave the best results was styrene-divinyl benzene however other phases were also investigated. The use of a single gas chromatography method was also investigated for the purpose of confirmatory identification of the VOC's. Various detection systems were used including MS and AED. It was shown that by optimising the GC's it was possible to get complimentary results. Also investigated was the possibility of compound tagging in an attempt to confirm the identity of several of the compounds found in the air. Chapter 5 is a theoretical discussion of the ways presenting the data obtained experimentally in an easy to understand way. Instead of targeting 7 or 8 compounds as being representative of air quality it is argued that by using a technique such as Air Fingerprinting, it is possible to show data that is indicative of the whole air sample. Using actual data it is possible to show the origin of the air sample in a simple yet effective way using air fingerprints.Also discussed is the Individual Component Air Quality Index, this is a method of quantifying air quality. By taking into account compound toxicity, atmospheric lifetime and UV exposure, the ICAQI, it is argued, is a technique that presents a more accurate picture of air quality.Chapter 6 concludes the thesis by drawing together the themes and issues that were raised.

Bioconcentration model for non-ionic, polar, and ionizable organic compounds in amphipod.

PubMed

Chen, Ciara Chun; Kuo, Dave Ta Fu

2018-05-01

The present study presents a bioconcentration model for non-ionic, polar, and ionizable organic compounds in amphipod based on first-order kinetics. Uptake rate constant k 1 is modeled as logk1=10.81logKOW + 0.15 (root mean square error [RMSE] = 0.52). Biotransformation rate constant k M is estimated using an existing polyparameter linear free energy relationship model. Respiratory elimination k 2 is calculated as modeled k 1 over theoretical biota-water partition coefficient K biow considering the contributions of lipid, protein, carbohydrate, and water. With negligible contributions of growth and egestion over a typical amphipod bioconcentration experiment, the bioconcentration factor (BCF) is modeled as k 1 /(k M  + k 2 ) (RMSE = 0.68). The proposed model performs well for non-ionic organic compounds (log K OW range = 3.3-7.62) within 1 log-unit error margin. Approximately 12% of the BCFs are underpredicted for polar and ionizable compounds. However, >50% of the estimated k 2 values are found to exceed the total depuration rate constants. Analyses suggest that these excessive k 2 values and underpredicted BCFs reflect underestimation in K biow , which may be improved by incorporating exoskeleton as a relevant partitioning component and refining the membrane-water partitioning model. The immediate needs to build up high-quality experimental k M values, explore the sorptive role of exoskeleton, and investigate the prevalence of k 2 overestimation in other bioconcentration models are also identified. The resulting BCF model can support, within its limitations, the ecotoxicological and risk assessment of emerging polar and ionizable organic contaminants in aquatic environments and advance the science of invertebrate bioaccumulation. Environ Toxicol Chem 2018;37:1378-1386. © 2018 SETAC. © 2018 SETAC.

Secondary organic aerosol formation and composition from the photo-oxidation of methyl chavicol (estragole)

NASA Astrophysics Data System (ADS)

Pereira, K. L.; Hamilton, J. F.; Rickard, A. R.; Bloss, W. J.; Alam, M. S.; Camredon, M.; Muñoz, A.; Vásquez, M.; Borrás, E.; Ródenas, M.

2013-12-01

The increasing demand for palm oil for uses in biofuel and food products is leading to rapid expansion of oil palm agriculture. Methyl chavicol (also known as estragole and 1-allyl-4-methoxybenzene) is an oxygenated biogenic volatile organic compound that was recently identified as the main floral emission from an oil palm plantation in Malaysian Borneo. The emissions of methyl chavicol observed may impact regional atmospheric chemistry, but little is known of its ability to form secondary organic aerosol (SOA). The photo-oxidation of methyl chavicol was investigated at the European Photoreactor chamber as a part of the atmospheric chemistry of methyl chavicol (ATMECH) project. Aerosol samples were collected using a particle into liquid sampler (PILS) and analysed offline using an extensive range of instruments including; high performance liquid chromatography mass spectrometry (HPLC-ITMS), high performance liquid chromatography quadrupole time-of-flight mass spectrometry (HPLC-QTOFMS) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The SOA yield was determined as 18-29% depending on initial precursor (VOC : NOx) mixing ratios. In total, 59 SOA compounds were observed and the structures of 10 compounds have been identified using high resolution tandem mass spectrometry. The addition of hydroxyl and/or nitro functional groups to the aromatic ring appears to be an important mechanistic pathway for aerosol formation. This results in the formation of compounds with both low volatility and high O : C ratios, where functionalisation rather than fragmentation is mainly observed as a~result of the stability of the ring. The SOA species observed can be characterized as semi-volatile to low volatile oxygenated organic aerosol (SVOOA and LVOOA) components and therefore may be important in aerosol formation and growth.

Transmission electron microscopy of unstained hybrid Au nanoparticles capped with PPAA (plasma-poly-allylamine): structure and electron irradiation effects.

PubMed

Gontard, Lionel C; Fernández, Asunción; Dunin-Borkowski, Rafal E; Kasama, Takeshi; Lozano-Pérez, Sergio; Lucas, Stéphane

2014-12-01

Hybrid (organic shell-inorganic core) nanoparticles have important applications in nanomedicine. Although the inorganic components of hybrid nanoparticles can be characterized readily using conventional transmission electron microscopy (TEM) techniques, the structural and chemical arrangement of the organic molecular components remains largely unknown. Here, we apply TEM to the physico-chemical characterization of Au nanoparticles that are coated with plasma-polymerized-allylamine, an organic compound with the formula C3H5NH2. We discuss the use of energy-filtered TEM in the low-energy-loss range as a contrast enhancement mechanism for imaging the organic shells of such particles. We also study electron-beam-induced crystallization and amorphization of the shells and the formation of graphitic-like layers that contain both C and N. The resistance of the samples to irradiation by high-energy electrons, which is relevant for optical tuning and for understanding the degree to which such hybrid nanostructures are stable in the presence of biomedical radiation, is also discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Giant magnetoresistive cobalt oxide compounds

DOEpatents

Schultz, Peter G.; Xiang, Xiaodong; Goldwasser, Isy

1998-01-01

Methods and apparatus for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties.

Giant magnetoresistive cobalt oxide compounds

DOEpatents

Schultz, P.G.; Xiang, X.; Goldwasser, I.

1998-07-07

Methods and apparatus are disclosed for the preparation and use of a substrate having an array of diverse materials in predefined regions thereon. A substrate having an array of diverse materials thereon is generally prepared by delivering components of materials to predefined regions on a substrate, and simultaneously reacting the components to form at least two materials. Materials which can be prepared using the methods and apparatus of the present invention include, for example, covalent network solids, ionic solids and molecular solids. More particularly, materials which can be prepared using the methods and apparatus of the present invention include, for example, inorganic materials, intermetallic materials, metal alloys, ceramic materials, organic materials, organometallic materials, non-biological organic polymers, composite materials (e.g., inorganic composites, organic composites, or combinations thereof), etc. Once prepared, these materials can be screened for useful properties including, for example, electrical, thermal, mechanical, morphological, optical, magnetic, chemical, or other properties. Thus, the present invention provides methods for the parallel synthesis and analysis of novel materials having useful properties. 58 figs.

Synthesis of Large Molecules in Cometary Ice Analogs: Physical Properties Related to Self-Assembly Processes

NASA Technical Reports Server (NTRS)

Dworkin, Jason P.; Sandford, Scott A.; Deamer, David W.; Gillette, J. Seb; Zare, Richard N.; Allamandola, Louis J. (Technical Monitor)

1999-01-01

The combination of realistic laboratory simulations and infrared observations have revolutionized our understanding of interstellar dust and ice-the main component of comets. Since comets and carbonaceous micrometeorites may have been important sources of volatiles and carbon compounds on the early Earth, their organic composition may be related to the origin of life. Ices on grains in molecular clouds contain a variety of simple molecules. The D/H ratios of the comets Hale-Bopp and Hyakutake are consistent with a primarily interstellar ice mixture. Within the cloud and especially in the presolar nebula through the early solar system, these icy grains would have been photoprocessed by the ultraviolet producing more complex species such as hexamethylenetetramine, polyoxymethylenes, and simple keones. We reported at the 1999 Bioastronomy meeting laboratory simulations studied to identify the types of molecules which could have been generated in pre-cometary ices. Experiments were conducted by forming a realistic interstellar mixed-molecular ice (H2O, CH3OH, NH3 and CO) at approximately 10 K under high vacuum irradiated with UV light from a hydrogen plasma lamp. The gas mixture was typically 100:50:1:1, however when different ratios were used material with similar characteristics was still produced. The residue that remained after warming to room temperature was analyzed by HPLC, and by several mass spectrometric methods. This material contains a rich mixture of complex compounds with mass spectral profiles resembling those found in IDPs and meteorites. Surface tension measurements show that an amphiphilic component is also present. These species do not appear in various controls or in unphotolyzed samples. Residues from the simulations were also dispersed in aqueous media for microscopy. The organic material forms 10-40 gm diameter droplets that fluoresce at 300-450 nm under UV excitation. These droplets have a morphology and internal structure which appear strikingly similar to those produced by extracts of the Murchison meteorite. Together, these results suggest a link between organic material photochemically synthesized on the cold grains in dense, interstellar molecular clouds and compounds that may have contributed to the organic inventory of the primitive Earth. For example, the amphiphilic properties of such compounds permit self-assembly into the membranous boundary structures that required for the first forms of cellular life.

The Biogeochemistry of Sulfur in Hydrothermal Systems

NASA Technical Reports Server (NTRS)

Schulte, Mitchell; Rogers, K. L.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. The incorporation of sulfur into many biomolecules likely dates back to the development of the earliest metabolic strategies. Sulfur is common in enzymes and co-enzymes and is an indispensable structural component in many peptides and proteins. Early metabolism may have been heavily influenced by the abundance of sulfide minerals in hydrothermal systems. Understanding how sulfur became prevalent in biochemical processes and many biomolecules requires knowledge of the reaction properties of sulfur-bearing compounds. We have previously estimated thermodynamic data for thiols, the simplest organic sulfur compounds, at elevated temperatures and pressures. If life began in hydrothermal environments, it is especially important to understand reactions at elevated temperatures among sulfur-bearing compounds and other organic molecules essential for the origin and persistence of life. Here we examine reactions that may have formed amino acids with thiols as reaction intermediates in hypothetical early Earth hydrothermal environments. (There are two amino acids, cysteine and methionine, that contain sulfur.) Our calculations suggest that significant amounts of some amino acids were produced in early Earth hydrothermal fluids, given reasonable concentrations H2, NH3, H2S and CO. For example, preliminary results indicate that glycine activities as high as 1 mmol can be reached in these systems at 100 C. Alanine formation from propanethiol is also a favorable reaction. On the other hand, the calculated equilibrium log activities of cysteine and serine from propanethiol are -21 and -19, respectively, at 100 C. These results indicate that while amino acid formation with thiols as intermediates is favored in some cases, other mechanisms may have been necessary to produce significant amounts of other amino acids. Coupled with our previous results for thiols, these studies imply that sulfur may have been easily incorporated into the organic geochemistry of early Earth hydrothermal systems, leading to its widespread use in biomolecules. Formation of more complex biomolecules in hydrothermal systems may have required sulfur-bearing organic compounds as reaction intermediates.

Mass spectrometry.

NASA Technical Reports Server (NTRS)

Burlingame, A. L.; Johanson, G. A.

1972-01-01

Review of the current state of mass spectrometry, indicating its unique importance for advanced scientific research. Mass spectrometry applications in computer techniques, gas chromatography, ion cyclotron resonance, molecular fragmentation and ionization, and isotope labeling are covered. Details are given on mass spectrometry applications in bio-organic chemistry and biomedical research. As the subjects of these applications are indicated alkaloids, carbohydrates, lipids, terpenes, quinones, nucleic acid components, peptides, antibiotics, and human and animal metabolisms. Particular attention is given to the mass spectra of organo-inorganic compounds, inorganic mass spectrometry, surface phenomena such as secondary ion and electron emission, and elemental and isotope analysis. Further topics include mass spectrometry in organic geochemistry, applications in geochronology and cosmochemistry, and organic mass spectrometry.

Geochemical interpretation of distribution of aromatic hydrocarbons in components of geologic environment of Pechora, Barents and Kara seas.

NASA Astrophysics Data System (ADS)

Kursheva, Anna; Petrova, Vera; Litvinenko, Ivan; Morgunova, Inna

2017-04-01

Information about the hydrocarbons content (including aromatic ones) in components of geologic environment allows to define common factors in distribution and correlation both nature and technogenic component, and also to reveal the sources of contamination. At that, it should be noted, that hydrocarbons are widely spread in lithosphere and create steady geochemical background, variations are caused here by specifics of initial organic matter, conditions of its accumulation and transformation. The basis of the study are the samples of sea water and deep sea sediments (more than 600 stations), collected in western sector of Arctic region (Pechora, Barents and Kara seas) during the scientific-research expeditions of FSBI "VNIIOkeangeologia" for the period 2000-2010. Total content of aromatic hydrocarbons was defined by spectrofluorometric method using analyzer «FLUORAT-Panorama-02». Certification of data was performed on representative samples based on contents and molecule structure of polycyclic aromatic hydrocarbons using GC-MS (Agilent 5973/6850 GC-MS System). Results of spectrofluorometric analysis of lipid fraction of organic matter of bottom sediments allowed to define specific parameters, which characterize various lithofacies groups of sediments. Thus, sandy residues are characterized by low level of aromatic hydrocarbons (ca. 4.3 μg/g) with prevalence of bi- and tri-aromatic compounds (λmax 270-310 nm). This correlates with low sorption capacity of coarse-grained sediments and absence of organic-mineral component, containing the breakdown products of initial organic matter. Tetra- and penta- aromatic structures prevail in clay sediments (ca. 13.0 μg/g), which are typical components of lipid fraction of organic matter of post sedimentation and early diagenetic stages of transformation. At that, changes of spectral characteristic of sediments in stratigraphic sequence completely reflect processes of diagenetic transformation of organic matter, including aromatization and new formation of number of compounds, for example perylene (λmax 405,435 nm). The presence in sediments of highly transformed (post-diagenetic) organic material forms special (for naphthides) type of spectrum (λmax 370-380 nm), which interface is fundamentally different from recent marine sediments. Similar type of spectrum in combination with anomalously high content of aromatic hydrocarbons (ca. 349.1 μg/g) is typical, in particular, for shelf of Spitsbergen archipelago, whose erosion and redeposition of carboniferous rocks play important role in deposits formation. Similar content of aromatic hydrocarbons was noted in sediments of shelf of the Island Kolguev, where exogenous anomaly is caused mainly by anthropogenic factors. This assumption correlates with the results of aromatic hydrocarbons examination where pyrogenic components dominate. The influence of endogenous processes (seepage of hydrocarbons) also may lead to substantial deformation of background spectrum due to formation of intensive peak in short-wave region (λmax max 240-260 nm). Credibility of collected results is proven by significant correlation of quantitative estimation of aromatic hydrocarbons contents conducted using both dispersed organic matter extraction and fractionation and spectrofluorimetry methods. Results, received during GC-MS analysis also prove spectrofluorometric information.

Release and microbial degradation of dissolved organic matter (DOM) from the macroalgae Ulva prolifera.

PubMed

Zhang, Tao; Wang, Xuchen

2017-12-15

Release and microbial degradation of dissolved organic matter (DOM) and chromophoric dissolved organic matter (CDOM) from the macroalgae Ulva prolifera were studied in laboratory incubation experiments. The release of DOM and CDOM from Ulva prolifera was a rapid process, and hydrolysis played an important role in the initial leaching of the organic compounds from the algae. Bacterial activity enhanced the release of DOM and CDOM during degradation of the algae and utilization of the released organic compounds. It is calculated that 43±2% of the C and 63±3% of the N from Ulva prolifera's biomass were released during the 20-day incubation, and 65±3% of the released C and 87±4% of the released N were utilized by bacteria. In comparison, only 18±1% of the algae's C and 17±1% of its N were released when bacterial activities were inhibited. The fluorescence characteristics of the CDOM indicate that protein-like DOM was the major organic component released from Ulva prolifera that was highly labile and biodegradable. Bacteria played an important role in regulating the chemical composition and fluorescence characteristics of the DOM. Our study suggests that the release of DOM from Ulva prolifera provides not only major sources of organic C and N, but also important food sources to microbial communities in coastal waters. Copyright © 2017 Elsevier Ltd. All rights reserved.

Organic component vapor pressures and hygroscopicities of aqueous aerosol measured by optical tweezers.

PubMed

Cai, Chen; Stewart, David J; Reid, Jonathan P; Zhang, Yun-hong; Ohm, Peter; Dutcher, Cari S; Clegg, Simon L

2015-01-29

Measurements of the hygroscopic response of aerosol and the particle-to-gas partitioning of semivolatile organic compounds are crucial for providing more accurate descriptions of the compositional and size distributions of atmospheric aerosol. Concurrent measurements of particle size and composition (inferred from refractive index) are reported here using optical tweezers to isolate and probe individual aerosol droplets over extended timeframes. The measurements are shown to allow accurate retrievals of component vapor pressures and hygroscopic response through examining correlated variations in size and composition for binary droplets containing water and a single organic component. Measurements are reported for a homologous series of dicarboxylic acids, maleic acid, citric acid, glycerol, or 1,2,6-hexanetriol. An assessment of the inherent uncertainties in such measurements when measuring only particle size is provided to confirm the value of such a correlational approach. We also show that the method of molar refraction provides an accurate characterization of the compositional dependence of the refractive index of the solutions. In this method, the density of the pure liquid solute is the largest uncertainty and must be either known or inferred from subsaturated measurements with an error of <±2.5% to discriminate between different thermodynamic treatments.

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota

NASA Astrophysics Data System (ADS)

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.; Kostka, Joel E.; Hanson, Paul; Chanton, Jeffrey P.

2018-02-01

We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur, and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and excitation-emission matrix parallel factor analysis components within the peat column. In particular, the intermediate depth zone ( 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate depth zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively, these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table, redox oscillation, and pore water advection.

Vertical Stratification of Peat Pore Water Dissolved Organic Matter Composition in a Peat Bog in Northern Minnesota: Pore Water DOM composition in a peat bog

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

Tfaily, Malak M.; Wilson, Rachel M.; Cooper, William T.

We characterized dissolved organic matter (DOM) composition throughout the peat column at the Marcell S1 forested bog in northern Minnesota and tested the hypothesis that redox oscillations associated with cycles of wetting and drying at the surface of the fluctuating water table correlate with increased carbon, sulfur and nitrogen turn over. We found significant vertical stratification of DOM molecular composition and EEM-PARAFAC components within the peat column. In particular the intermediate depth zone (~ 50 cm) was identified as a zone where maximum decomposition and turnover is taking place. Surface DOM was dominated by inputs from surface vegetation. The intermediate-depthmore » zone was an area of high organic matter reactivity and increased microbial activity with diagenetic formation of many unique compounds, among them polycyclic aromatic compounds (PAC) that contain both nitrogen and sulfur heteroatoms. These compounds have been previously observed in coal-derived compounds and were assumed to be responsible for coal's biological activity. Biological processes triggered by redox oscillations taking place at the intermediate depth zone of the peat profile at the S1 bog are assumed to be responsible for the formation of these heteroatomic PACs in this system. Alternatively these compounds could stem from black carbon and nitrogen derived from fires that have occurred at the site in the past. Surface and deep DOM exhibited more similar characteristics, compared to the intermediate-depth zone, with the deep layer exhibiting greater input of microbially degraded organic matter than the surface suggesting that the entire peat profile consists of similar parent material at different degrees of decomposition and that lateral and vertical advection of pore water from the surface to the deeper horizons is responsible for such similarities. Our findings suggest that molecular composition of DOM in peatland pore water is dynamic and is a function of ecosystem activity, water table and redox oscillation and porewater advection.« less

Two Isomeric C16 Oxo-Fatty Acids from the Diatom Chaetoceros karianus Show Dual Agonist Activity towards Human Peroxisome Proliferator-Activated Receptors (PPARs) α/γ

PubMed Central

Moldes-Anaya, Angel; Sæther, Thomas; Uhlig, Silvio; Nebb, Hilde I.; Larsen, Terje; Eilertsen, Hans C.; Paulsen, Steinar M.

2017-01-01

The peroxisome proliferator-activated receptors (PPARs) function as ligand-activated transcription factors that convert signals in the form of lipids to physiological responses through the activation of metabolic target genes. Due to their key roles in lipid and carbohydrate metabolism, the PPARs are important drug targets. However, for several of the PPAR drugs currently in use, adverse side effects have been reported. In an effort to identify compounds from marine organisms that may serve as molecular scaffolds for the development of novel and safer PPAR-targeting drugs, we performed a bioassay-guided screening of organic extracts made from organisms supplied by the Norwegian Biobank of Arctic Marine Organisms (Marbank). Among several interesting hits, we identified two poorly described isomeric oxo-fatty acids from the microalgae Chaetoceros karianus for which we provide the first evidence that they might display dual specificity towards human PPARα and PPARγ. Principal component analysis showed that C. karianus stood out from other Chaetoceros species, both with respect to the metabolic profile and the PPAR activity. The isolation of these compounds holds the potential of uncovering a PPAR pharmacophore with tunable activity and specificity. PMID:28587091

BitterDB: a database of bitter compounds

PubMed Central

Wiener, Ayana; Shudler, Marina; Levit, Anat; Niv, Masha Y.

2012-01-01

Basic taste qualities like sour, salty, sweet, bitter and umami serve specific functions in identifying food components found in the diet of humans and animals, and are recognized by proteins in the oral cavity. Recognition of bitter taste and aversion to it are thought to protect the organism against the ingestion of poisonous food compounds, which are often bitter. Interestingly, bitter taste receptors are expressed not only in the mouth but also in extraoral tissues, such as the gastrointestinal tract, indicating that they may play a role in digestive and metabolic processes. BitterDB database, available at http://bitterdb.agri.huji.ac.il/bitterdb/, includes over 550 compounds that were reported to taste bitter to humans. The compounds can be searched by name, chemical structure, similarity to other bitter compounds, association with a particular human bitter taste receptor, and so on. The database also contains information on mutations in bitter taste receptors that were shown to influence receptor activation by bitter compounds. The aim of BitterDB is to facilitate studying the chemical features associated with bitterness. These studies may contribute to predicting bitterness of unknown compounds, predicting ligands for bitter receptors from different species and rational design of bitterness modulators. PMID:21940398

Thermal alterations of organic matter in coal wastes from Upper Silesia, Poland

NASA Astrophysics Data System (ADS)

Misz-Kennan, Magdalena

2010-01-01

Self-heating and self-combustion are currently taking place in some coal waste dumps in the Upper Silesian Coal Basin, Poland, e.g. the dumps at Rymer Cones, Starzykowiec, and the Marcel Coal Mine, all in the Rybnik area. These dumps are of similar age and self-heating and combustion have been occurring in all three for many years. The tools of organic petrography (maceral composition, rank, etc.), gas chromatography-mass spectrometry, and proximate and ultimate analysis are used to investigate the wastes. Organic matter occurs in quantities up to 85 vol.%, typically a few to several vol.%, in the wastes. All three maceral groups (vitrinite, liptinite, and inertinite) are present as unaltered and variously-altered constituents associated with newly-formed petrographic components (bitumen expulsions, pyrolytic carbon). The predominant maceral group is vitrinite with alterations reflected in the presence of irregular cracks, oxidation rims and, rarely, devolatilisation pores. In altered wastes, paler grey-vitrinite and/or coke dominates. The lack of plasticity, the presence of paler-coloured particles, isotropic massive coke, dispersed coked organic matter, and expulsions of bitumens all indicate that heating was slow and extended over a long time. Macerals belonging to other groups are present in unaltered form or with colours paler than the colours of the parent macerals. Based on the relative contents of organic compounds, the most important groups of these identified in the wastes are n-alkanes, acyclic isoprenoids, hopanes, polycyclic aromatic hydrocarbons (PAHs) and their derivatives, phenol and its derivatives. These compounds occur in all wastes except those most highly altered where they were probably destroyed by high temperatures. These compounds were generated mainly from liptinite-group macerals. Driven by evaporation and leaching, they migrated within and out of the dump. Their presence in some wastes in which microscopically visible organic matter is lacking suggests that they originated elsewhere and subsequently migrated through the dump piles. During their migration, the compounds fractionated, were adsorbed on minerals and/or interacted. The absence of alkenes, and of other unsaturated organic compounds, may reflect primary diagenetic processes that occurred in coals and coal shales during burial and/or organic matter type. Their absence may also be a consequence of heating that lasted many years, hydropyrolysis, and/or the participation of minerals in the reactions occurring within the dumps. The wastes contain compounds typical of organic matter of unaltered kerogen III type and the products of pyrolytic processes, and mixtures of both. In some wastes, organic compounds are completely absent having been destroyed by severe heating. The distributions of n-alkanes in many samples are typical of pyrolysates. In some wastes, narrow n-alkane distributions reflect their generation over small temperature ranges. In others, wider distributions point to greater temperature ranges. Other wastes contain n-alkane distributions typical of unaltered coal and high pristane content or mixtures of pyrolysates and unaltered waste material. The wastes also contain significant amounts of final αβ hopanes. Polycyclic aromatic hydrocarbons are represented only by two- to five-ring compounds as is typical of the thermal alteration of hard coal. Correlations between the degree of organic matter alteration and the relative contents of individual PAHs and hopanes and geochemical indicators of thermal alteration are generally poor. The properties of the organic matter (its composition and rank), temperature fluctuations within the dumps, migration of organic compounds and mineral involvement are probably responsible for this. The processes taking place in coal waste dumps undergoing self-heating and self-combustion are complicated; they are very difficult to estimate and define. The methods of organic petrology and geochemistry give complementary data allowing the processes to be described. However, each of the dumps investigated represents a separate challenge to be surmounted in any regional attempt to delineate the regional environmental impact of these waste dumps.

Ultrabright fluorescent OLEDS using triplet sinks

DOEpatents

Zhang, Yifan; Forrest, Stephen R; Thompson, Mark

2013-06-04

A first device is provided. The first device further comprises an organic light emitting device. The organic light emitting device further comprises an anode, a cathode, and an emissive layer disposed between the anode and the cathode. The emissive layer further comprises an organic host compound, an organic emitting compound capable of fluorescent emission at room temperature, and an organic dopant compound. The triplet energy of the dopant compound is lower than the triplet energy of the host compound. The dopant compound does not strongly absorb the fluorescent emission of the emitting compound.

δ 13C of free and macromolecular aromatic structures in the murchison meteorite

NASA Astrophysics Data System (ADS)

Sephton, M. A.; Pillinger, C. T.; Gilmour, I.

1998-05-01

Analyses of the organic compounds in the Murchison meteorite have led to a greater understanding of the nature of extraterrestrial organic materials. However, the relationship between low and high molecular weight material remains poorly understood. To investigate this relationship, untreated Murchison was subjected to supercritical fluid extraction (SFE) to obtain the free organic components in the meteorite. Toluene and other volatile aromatic hydrocarbons dominated the extract, and the carbon isotopic composition of these molecules was determined by gas chromatography-isotope ratio-mass spectrometry (GCIRMS). δ 13C values of the aromatic hydrocarbons ranged from -28.8 to -5.8‰. These compounds displayed a 13C-enrichment with increasing carbon number suggesting an origin by cracking. The high molecular weight organic material in the meteorite was isolated and subjected to hydrous pyrolysis. This procedure produced a number of aromatic products, the majority of which were volatile aromatic hydrocarbons, particularly toluene. SFE was used to extract and successfully retain them. This enabled the first carbon isotopic analysis of this poorly understood material to be performed at the molecular level by GCIRMS. δ 13C values for aromatic pyrolysis products occupied a range from -24.6 to -5.6‰. The trend of 13C-enrichment with increasing carbon number, observed in the free compounds, was also evident in the macromolecular fragments. Furthermore, the organic fragments of the macromolecular material were consistently 13C-enriched when compared to structurally identical free molecules. This suggested that the free aromatic hydrocarbons in Murchison were produced by the preterrestrial degradation of the organic macromolecular material. This natural degradation event was extended by the hydrous pyrolysis experiment.

Immunotoxicity in green mussels under perfluoroalkyl substance (PFAS) exposure: Reversible response and response model development.

PubMed

Liu, Changhui; Gin, Karina Yew-Hoong

2018-04-01

The immunotoxicity of 4 commonly detected perfluoroalkyl substances (PFASs), namely, perfluorooctanesulfonate (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorodecanoic acid (PFDA) was investigated by measuring biomarkers of the immune profile of green mussels, Perna viridis. The biomarkers included neutral red retention, phagocytosis, and spontaneous cytotoxicity, all of which were tested on mussel hemocytes. Hemocytes are an important component of the invertebrate immune system. We found that exposure to PFASs could lead to reduced hemocyte cell viability and suppress immune function by up to 50% of normal performance within the experimental exposure range. The results indicate that PFASs have an immunotoxic potential and thus could pose severe health risks to aquatic organisms. The reported immunotoxicity is likely to result from the compounds' direct and indirect interactions with the hemocyte membrane, and therefore likely to affect the functionality of these cells. The immunotoxic response was found to be related to the organism's burden of PFASs, and was reversible when the compounds were removed from the test organisms. Based on this relationship, models using an organism's PFAS concentration and bioaccumulation factor (BAF) as the independent variables were established to quantify PFAS-induced immunotoxicity. The models help us to gain a better understanding of the toxic mechanism of PFASs, and provide a tool to evaluate adverse effects for the whole group of compounds with one mathematical equation. Environ Toxicol Chem 2018;37:1138-1145. © 2018 SETAC. © 2018 SETAC.

In Situ Formation Of Reactive Barriers For Pollution Control

DOEpatents

Gilmore, Tyler J.; Riley, Robert G.

2004-04-27

A method of treating soil contamination by forming one or more zones of oxidized material in the path of percolating groundwater is disclosed. The zone or barrier region is formed by delivering an oxidizing agent into the ground for reaction with an existing soil component. The oxidizing agent modifies the existing soil component creating the oxidized zone. Subsequently when soil contaminates migrate into the zone, the oxidized material is available to react with the contaminates and degrade them into benign products. The existing soil component can be an oxidizable mineral such as manganese, and the oxidizing agent can be ozone gas or hydrogen peroxide. Soil contaminates can be volatile organic compounds. Oxidized barriers can be used single or in combination with other barriers.

Characterization of the antibiotic compound no. 70 produced by Streptomyces sp. IMV-70.

PubMed

Trenozhnikova, Lyudmila P; Khasenova, Almagul K; Balgimbaeva, Assya S; Fedorova, Galina B; Katrukha, Genrikh S; Tokareva, Nina L; Kwa, Boo H; Azizan, Azliyati

2012-01-01

We describe the actinomycete strain IMV-70 isolated from the soils of Kazakhstan, which produces potent antibiotics with high levels of antibacterial activity. After the research of its morphological, chemotaxonomic, and cultural characteristics, the strain with potential to be developed further as a novel class of antibiotics with chemotherapeutics potential was identified as Streptomyces sp. IMV-70. In the process of fermentation, the strain Streptomyces spp. IMV-70 produces the antibiotic no. 70, which was isolated from the culture broth by extraction with organic solvents. Antibiotic compound no. 70 was purified and separated into individual components by HPLC, TLC, and column chromatography methods. The main component of the compound is the antibiotic 70-A, which was found to be identical to the peptolide etamycin A. Two other antibiotics 70-B and 70-C have never been described and therefore are new antibiotics. The physical-chemical and biological characteristics of these preparations were described and further researched. Determination of the optimal growth conditions to cultivate actinomycete-producer strain IMV-70 and development of methods to isolate, purify, and accumulate preparations of the new antibiotic no. 70 enable us to research further the potential of this new class of antibiotics.

Characterization of the Antibiotic Compound No. 70 Produced by Streptomyces sp. IMV-70

PubMed Central

Trenozhnikova, Lyudmila P.; Khasenova, Almagul K.; Balgimbaeva, Assya S.; Fedorova, Galina B.; Katrukha, Genrikh S.; Tokareva, Nina L.; Kwa, Boo H.; Azizan, Azliyati

2012-01-01

We describe the actinomycete strain IMV-70 isolated from the soils of Kazakhstan, which produces potent antibiotics with high levels of antibacterial activity. After the research of its morphological, chemotaxonomic, and cultural characteristics, the strain with potential to be developed further as a novel class of antibiotics with chemotherapeutics potential was identified as Streptomyces sp. IMV-70. In the process of fermentation, the strain Streptomyces spp. IMV-70 produces the antibiotic no. 70, which was isolated from the culture broth by extraction with organic solvents. Antibiotic compound no. 70 was purified and separated into individual components by HPLC, TLC, and column chromatography methods. The main component of the compound is the antibiotic 70-A, which was found to be identical to the peptolide etamycin A. Two other antibiotics 70-B and 70-C have never been described and therefore are new antibiotics. The physical-chemical and biological characteristics of these preparations were described and further researched. Determination of the optimal growth conditions to cultivate actinomycete-producer strain IMV-70 and development of methods to isolate, purify, and accumulate preparations of the new antibiotic no. 70 enable us to research further the potential of this new class of antibiotics. PMID:22536145

High-performance liquid chromatography of quinoidal imminium compounds derived from triphenylmethanes

USGS Publications Warehouse

Abidi, S.L.

1983-01-01

A series of eleven p-aminotriphenylmethane dyes have been studied by high-performance liquid chromatography (HPLC). The combined use of HPLC and spectrophotometry permits specific detection of these compounds in the visible range around 600 nm. As the high affinity of the imminium cations for the active sites of the hydrocarbonaceous stationary phase has presented difficulties for reversed-phase HPLC with pure solvents, organic electrolytes were added to the mobile phase to facilitate the elution of the components with improved selectivity, sensitivity (minimum detection limit, 0.1 μg/ml), and peak symmetry. The effects of chromatographic variables on the component retentivity were investigated. Retention times of the dye analytes decreased with increasing concentration of the added ionic reagent and with decreasing number of the hydrophobic alkyl substituents on the nitrogen atom. The influence of pH on the retention parameters appears to parallel that observed previously for cationic quaternary ammonium compounds. Among the acidic reagents employed, naphthalenesulfonic acid yielded the most satisfactory results. The use of binary electrolyte systems invariably improved the chromatographic behavior of the imminium solutes analyzed. Results obtained with two different octadecylsilica columns have been compared.

Development of Toxicity Benchmarks and Bioaccumulation Data for N-based Organic Explosives for Terrestrial Plants and Soil Invertebrates

DTIC Science & Technology

2012-11-01

studies ................................ 205 Table 88. Distribution of the radioactivity between the soil, plant tissue, and mineralization ...the environment. The fate of these compounds is dependent upon the sum of all processes leading to their sequestration or elimination. Such...likely due to its very low concentrations in soil. 7 2.3. Effects of energetics on soil biological activity Microbes are essential components of

Seasonal Changes of DOC Composition of Rivers in Temperate Monsoon Climates

NASA Astrophysics Data System (ADS)

Oh, N. H.; Shin, Y.; Lee, E. J.; Hur, J.

2014-12-01

The spatial and seasonal dynamics of dissolved organic carbon (DOC) composition and biodegradability were investigated for the five largest rivers in the Republic of Korea during the years 2012 - 2013 using dark incubation experiments and spectroscopic measurements, including parallel factor analysis (PARAFAC). The DOC concentrations of the rivers in relatively steep and forest-dominated basins were <~2 mg L-1, and remained relatively constant over the seasons. In contrast, those of the rivers influenced by urban and agricultural activities rose up to 5.4 mg L-1, which was decreased to ~2 mg L-1 during the summer monsoon period, indicating that increased precipitation had the effect of dilution. Among the fluorescence components, terrestrial humic-like components were dominant in all the rivers except for one, where tyrosine- or tryptophan-like compounds were the major component. However, terrestrial humic-like components became dominant in all five of the rivers after high precipitation which occurred during the monsoon season, during which ~76% of the annual precipitation was received. Considering that 64% of South Korea is forested, our results suggest that the forests could be a large source of riverine DOC, elevating the DOC loads during monsoon rainfall. Although more DOC could be degraded when DOC input increased, regardless of its sources, the percent biodegradability was reduced with increased proportions of terrestrially derived and aromatic compounds. These results suggest that the relatively stable and terrestrial humic-like compounds released during the monsoon rainfall could reduce the potential of microbial respiration of riverine DOC and evasion of river CO2 to the atmosphere, despite of the increase in the DOC load.

Geochemical characteristics of organic compounds in a permafrost sediment core sample from northeast Siberia, Russia

NASA Technical Reports Server (NTRS)

Matsumoto, G. I.; Friedmann, E. I.; Gilichinsky, D. A.

1995-01-01

We studied total organic carbon (TOC), hydrocarbons and fatty acids in a permafrost sediment core sample (well 6-90, length 32.0 m, 1.5-2.5 Ma BP) from northeast Siberia (approximately 70 degrees N, 158 degrees E), Russia, to elucidate their geochemical features in relation to source organisms and paleoenvironmental conditions. Long-chain n-alkanes and n-alkanoic acids (>C19) were most predominant hydrocarbons and fatty acids, respectively, so organic matter in the sediment core was derived mainly from vascular plants and, to a much smaller extent, from bacteria. Low concentrations of unsaturated fatty acids revealed that organic matter in the sediment core was considerably degraded during and/or after sedimentation. The predominance of vascular plant components, the major ionic components of nonmarine sources, and geological data strongly implied that the sediment layers were formed in shallow lacustrine environments, such as swamp with large influences of tundra or forest-tundra vegetation. Also, no drastic changes in paleoenvironmental conditions for biological activity or geological events, such as sea transgressions or ice-sheet influences, occurred at the sampling site approximately 100 km from the coast of the East Siberian Sea during the late Pliocene an early Pleistocene periods.

Periodic Vesicle Formation in Tectonic Fault Zones--an Ideal Scenario for Molecular Evolution.

PubMed

Mayer, Christian; Schreiber, Ulrich; Dávila, María J

2015-06-01

Tectonic fault systems in the continental crust offer huge networks of interconnected channels and cavities. Filled mainly with water and carbon dioxide (CO2), containing a wide variety of hydrothermal chemistry and numerous catalytic surfaces, they may offer ideal reaction conditions for prebiotic chemistry. In these systems, an accumulation zone for organic compounds will develop at a depth of approximately 1 km where CO2 turns sub-critical and dissolved components precipitate. At this point, periodic pressure changes caused for example by tidal influences or geyser activity may generate a cyclic process involving repeated phase transitions of carbon dioxide. In the presence of amphiphilic compounds, this will necessarily lead to the transient formation of coated water droplets in the gas phase and corresponding vesicular structures in the aqueous environment. During this process, the concentration of organic components inside the droplets and vesicles would be drastically increased, allowing for favorable reaction conditions and, in case of the vesicles generated, large trans-membrane concentration gradients. Altogether, the process of periodic formation and destruction of vesicles could offer a perfect environment for molecular evolution in small compartments and for the generation of protocells. The basic process of vesicle formation is reproduced experimentally with a lipid in a water/CO2 system.

The importance of quality control in validating concentrations ...

EPA Pesticide Factsheets

A national-scale survey of 247 contaminants of emerging concern (CECs), including organic and inorganic chemical compounds, and microbial contaminants, was conducted in source and treated drinking water samples from 25 treatment plants across the United States. Multiple methods were used to determine these CECs, including six analytical methods to measure 174 pharmaceuticals, personal care products, and pesticides. A three-component quality assurance/quality control (QA/QC) program was designed for the subset of 174 CECs which allowed us to assess and compare performances of the methods used. The three components included: 1) a common field QA/QC protocol and sample design, 2) individual investigator-developed method-specific QA/QC protocols, and 3) a suite of 46 method comparison analytes that were determined in two or more analytical methods. Overall method performance for the 174 organic chemical CECs was assessed by comparing spiked recoveries in reagent, source, and treated water over a two-year period. In addition to the 247 CECs reported in the larger drinking water study, another 48 pharmaceutical compounds measured did not consistently meet predetermined quality standards. Methodologies that did not seem suitable for these analytes are overviewed. The need to exclude analytes based on method performance demonstrates the importance of additional QA/QC protocols. This paper compares the method performance of six analytical methods used to measure 174 emer

Stabilizing metal components in electrodes of electrochemical cells

DOEpatents

Spengler, Charles J.; Ruka, Roswell J.

1989-01-01

Disclosed is a method of reducing the removal or transfer into a gas phase of a current carrying metal in an apparatus, such as an electrochemical cell 2 having a porous fuel electrode 6 containing metal particles 11, where the metal is subject to removal or transfer into a gaseous phase, the method characterized in that (1) a metal organic compound that decomposes to form an electronically conducting oxide coating when heated is applied to the metal and porous electrode, and (2) the compound on the metal is then heated to a temperature sufficient to decompose the compound into an oxide coating 13 by increasing the temperature at a rate that is longer than 1 hour between room temperature and 600.degree. C., resulting in at least one continuous layer 13, 14 of the oxide coating on the metal.

National Institute for Petroleum and Energy Research quarterly technical report, July 1--September 30, 1992. [Dinitrogen compound 1,10-phenanthroline

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

Not Available

Progress reports are presented for the following two fuel research programs: (1) development of analytical methodology for analysis of heavy crudes; and (2) thermochemistry and thermophysical properties of organic nitrogen and diheteroatom-containing compounds. For the first research program, gasoline range (82--43[degree]) components in liquid products from catalytic cracking whole Wilmington >650[degree]F resid, Wilmington >650[degree]F neutrals, and blends of neutrals plus 650--1000[degree]F acids and bases were determined by gas chromatography/mass spectroscopy. For the second research program, density measurements were completed for thianthrene between 450 K and near 570 K, and for phenoxathiin between 348 K and 548 K. Heat capacity measurementsmore » were begun for the dinitrogen compound 1,10-phenanthroline.« less

Multiple Cosmic Sources for Meteorite Macromolecules?

PubMed Central

Watson, Jonathan S.; Meredith, William; Love, Gordon D.; Gilmour, Iain; Snape, Colin E.

2015-01-01

Abstract The major organic component in carbonaceous meteorites is an organic macromolecular material. The Murchison macromolecular material comprises aromatic units connected by aliphatic and heteroatom-containing linkages or occluded within the wider structure. The macromolecular material source environment remains elusive. Traditionally, attempts to determine source have strived to identify a single environment. Here, we apply a highly efficient hydrogenolysis method to liberate units from the macromolecular material and use mass spectrometric techniques to determine their chemical structures and individual stable carbon isotope ratios. We confirm that the macromolecular material comprises a labile fraction with small aromatic units enriched in 13C and a refractory fraction made up of large aromatic units depleted in 13C. Our findings suggest that the macromolecular material may be derived from at least two separate environments. Compound-specific carbon isotope trends for aromatic compounds with carbon number may reflect mixing of the two sources. The story of the quantitatively dominant macromolecular material in meteorites appears to be made up of more than one chapter. Key Words: Abiotic organic synthesis—Carbonaceous chondrite—Cosmochemistry—Meteorites. Astrobiology 15, 779–786. PMID:26418568

A shape tailored gold-conductive polymer nanocomposite as a transparent electrode with extraordinary insensitivity to volatile organic compounds (VOCs)

PubMed Central

Khalil, Rania; Homaeigohar, Shahin; Häußler, Dietrich; Elbahri, Mady

2016-01-01

In this study, the transparent conducting polymer of poly (3,4-ethylenendioxythiophene): poly(styrene sulphonate) (PEDOT:PSS) was nanohybridized via inclusion of gold nanofillers including nanospheres (NSs) and nanorods (NRs). Such nanocomposite thin films offer not only more optimum conductivity than the pristine polymer but also excellent resistivity against volatile organic compounds (VOCs). Interestingly, such amazing properties are achieved in the diluted regimes of the nanofillers and depend on the characteristics of the interfacial region of the polymer and nanofillers, i.e. the aspect ratio of the latter component. Accordingly, a shape dependent response is made that is more desirable in case of using the Au nanorods with a much larger aspect ratio than their nanosphere counterparts. This transparent nanocomposite thin film with an optimized conductivity and very low sensitivity to organic gases is undoubtedly a promising candidate material for the touch screen panel production industry. Considering PEDOT as a known material for integrated electrodes in energy saving applications, we believe that our strategy might be an important progress in the field. PMID:27654345

Assessment of the Interstellar Processes Leading to Deuterium Enrichment in Meteoritic Organics

NASA Technical Reports Server (NTRS)

Sandford, Scott A.; Bernstein, Max P.; Dworkin, Jason P.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low temperature gas phase ion-molecule reactions, low temperature gas-grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D-enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, 0, and N in the same compounds.

Occurrence and sources of natural and anthropogenic lipid tracers in surface soils from arid urban areas of Saudi Arabia.

PubMed

Rushdi, Ahmed I; Al-Mutlaq, Khalid F; El-Mubarak, Aarif H; Al-Saleh, Mohammed A; El-Otaibi, Mubarak T; Ibrahim, Sami M M; Simoneit, Bernd R T

2016-01-01

Soil particles contain a variety of natural and anthropogenic organic components, and in urban areas can be considered as local collectors of pollutants. Surface soil samples were taken from ten urban areas in Riyadh during early winter of 2007. They were extracted with dichloromethane-methanol mixture and the extracts were analyzed by gas chromatography-mass spectrometry. The major compounds were unresolved complex mixture (UCM), plasticizers, n-alkanes, carbohydrates, n-alkanoic acids, hopanes, n-alkanols, and sterols. Vegetation detritus was the major natural source of organic compounds (24.0 ± 15.7%) in samples from areas with less human activities and included n-alkanes, n-alkanoic acids, n-alkanols, sterols and carbohydrates. Vehicular emission products and discarded plastics were the major anthropogenic sources in the soil particles (53.3 ± 21.3% and 22.7 ± 10.7%, respectively). The anthropogenic tracers were UCM, plasticizers, n-alkanes, hopanes and traces of steranes. Vegetation and human activities control the occurrence and distribution of natural and anthropogenic extractable organic matter in this arid urban area. Copyright © 2015 Elsevier Ltd. All rights reserved.

Formation of mixed organic layers by stepwise electrochemical reduction of diazonium compounds.

PubMed

Santos, Luis; Ghilane, Jalal; Lacroix, Jean Christophe

2012-03-28

This work describes the formation of a mixed organic layer covalently attached to a carbon electrode. The strategy adopted is based on two successive electrochemical reductions of diazonium salts. First, bithiophene phenyl (BTB) diazonium salt is reduced using host/guest complexation in a water/cyclodextrin (β-CD) solution. The resulting layer consists of grafted BTB oligomers and cyclodextrin that can be removed from the surface. The electrochemical response of several outer-sphere redox probes on such BTB/CD electrodes is close to that of a diode, thanks to the easily p-dopable oligo(BTB) moieties. When CD is removed from the surface, pinholes are created and this diode like behavior is lost. Following this, nitrophenyl (NP) diazonium is reduced to graft a second component. Electrochemical study shows that upon grafting NP insulating moieties, the diode-like behavior of the layer is restored which demonstrates that NP is grafted predominately in the empty spaces generated by β-CD desorption. As a result, a mixed BTB/NP organic layer covalently attached to a carbon electrode is obtained using a stepwise electrochemical reduction of two diazonium compounds.

Modeling study of secondary organic aerosol in winter in China using NAQPMS

NASA Astrophysics Data System (ADS)

Yang, W.; Li, J.

2017-12-01

The concentration of organic aerosol (OA) in the central and eastern China is much higher than that in Europe and America. Compared with the observation, the current numerical modeling studies largely underestimated the concentration of OA, especially the secondary component. Based on the volatility basis set framework, a secondary organic aerosol (SOA) module was developed, which considering the multi-generation oxidation of volatile organic compounds (VOCs), semi-volatile POA and intermediate volatility organic compounds (IVOCs). The newly developed SOA module was coupled into the NAQPMS, and the performance of the simulation was validated by the observation with high temporal resolution. In wintertime, the OA concentration in the central and eastern China was maintained above 15-20 μg·m-3, and SOA accounted for 50-65% of OA concentration. The OA concentration even reached 40 μg·m-3 in the provinces emitting most pollutants (such as Hunan, Hubei, Henan, Anhui, Jiangsu, Shandong and Hubei province). IVOCs were important precursors of SOA in China, and could reduce the great discrepancy between simulation and observation. In wintertime, the contribution from IVOCs accounted for 60-80% of SOA formation. The aging of semi-volatile POA had less impact on the SOA formation, which maintained only 2-8% over central and eastern China.

Measurements of Size Resolved Organic Particulate Mass Using An On-line Aerosol Mass Spectrometer (ams) Laboratory Validation; Analysis Tool Development; and Interpretation of Field Data

NASA Astrophysics Data System (ADS)

Alfarra, M. R.; Coe, H.; Allan, J. D.; Bower, K. N.; Garforth, A. A.; Canagaratna, M.; Worsnop, D.

The aerosol mass spectrometer (AMS) is a quantitative instrument designed to deliver real-time size resolved chemical composition of the volatile and semi volatile aerosol fractions. The AMS response to a wide range of organic compounds has been exper- imentally characterized, and has been shown to compare well with standard libraries of 70 eV electron impact ionization mass spectra. These results will be presented. Due to the scanning nature of the quadrupole mass spectrometer, the AMS provides averaged composition of ensemble of particles rather than single particle composi- tion. However, the mass spectra measured by AMS are reproducible and similar to those of standard libraries so analysis tools can be developed on large mass spectral libraries that can provide chemical composition information about the type of organic compounds in the aerosol. One such tool is presented and compared with laboratory measurements of single species and mixed component organic particles by the AMS. We will then discuss the applicability of these tools to interpreting field AMS data ob- tained in a range of experiments at different sites in the UK and Canada. The data will be combined with other measurements to show the behaviour of the organic aerosol fraction in urban and sub-urban environments.

Generation and validation of oxygenated volatile organic carbon standards for the 1995 Southern Oxidants Study Nashville Intensive

NASA Astrophysics Data System (ADS)

Apel, E. C.; Calvert, J. G.; Greenberg, J. P.; Riemer, D.; Zika, R.; Kleindienst, T. E.; Lonneman, W. A.; Fung, K.; Fujita, E.

1998-09-01

Two volatile organic compound (VOC) mixtures were made available and utilized for the calibration of instruments and intercomparison exercises at the Youth, Inc. (YI) site during the Southern Oxidants Study Nashville Intensive. Cylinder 1, made by Scott-Marrin, Inc., contained 14 components (3 nonmethane hydrocarbons (NMHCs) and 11 oxygen-containing VOCs (OVOCs)) and is referred to as OVOCl. Cylinder 2, made at the National Center for Atmospheric Research (NCAR), contained 4 components (one NMHC and three OVOCs) and is referred to as OVOC2. The mixtures were not prepared by either laboratory as primary standards but significant effort was applied to validate their concentrations by several different laboratories using several different techniques. The mixtures were prepared in high-pressure cylinders in the parts per million by volume (ppmv) range using calibrated syringe methods. Gas Chromatographic (GC) and 2,4-dinitrophenylhydrazine (DNPH) cartridge/high-pressure liquid Chromatographic (HPLC) systems were utilized in the calibration of the cylinders. GC detectors included the flame ionization detector (FID) and atomic emission detector (AED). Results obtained with the GC/FID systems for OVOCs were adjusted in terms of the effective carbon number (ECN), obtained from literature values, to correct for the reduced response of the FID for compounds containing oxygen, relative to compounds containing only carbon and hydrogen. Cylinder concentrations were derived and compared based on the ECN-adjusted FID results, the AED results, and the DNPH cartridge results. The various methods employed agreed to within approximately 15%. Both cylinders were stable (±4%) over a period of 2 years.

Volatility of organic aerosol and its components in the Megacity of Paris

NASA Astrophysics Data System (ADS)

Paciga, A.; Karnezi, E.; Kostenidou, E.; Hildebrandt, L.; Psichoudaki, M.; Engelhart, G. J.; Lee, B.-H.; Crippa, M.; Prévôt, A. S. H.; Baltensperger, U.; Pandis, S. N.

2015-08-01

Using a mass transfer model and the volatility basis set, we estimate the volatility distribution for the organic aerosol (OA) components during summer and winter in Paris, France as part of the collaborative project MEGAPOLI. The concentrations of the OA components as a function of temperature were measured combining data from a thermodenuder and an aerosol mass spectrometer (AMS) with Positive Matrix Factorization (PMF) analysis. The hydrocarbon-like organic aerosol (HOA) had similar volatility distributions for the summer and winter campaigns with half of the material in the saturation concentration bin of 10 μg m-3 and another 35-40 % consisting of low and extremely low volatility organic compounds (LVOCs and ELVOCs, respectively). The winter cooking OA (COA) was more than an order of magnitude less volatile than the summer COA. The low volatility oxygenated OA (LV-OOA) factor detected in the summer had the lowest volatility of all the derived factors and consisted almost exclusively of ELVOCs. The volatility for the semi-volatile oxygenated OA (SV-OOA) was significantly higher than that of the LV-OOA, containing both semi-volatile organic components (SVOCs) and LVOCs. The oxygenated OA (OOA) factor in winter consisted of SVOCs (45 %), LVOCs (25 %) and ELVOCs (30 %). The volatility of marine OA (MOA) was higher than that of the other factors containing around 60 % SVOCs. The biomass burning OA (BBOA) factor contained components with a wide range of volatilities with significant contributions from both SVOCs (50 %) and LVOCs (30 %). Finally, combining the O : C ratio and volatility distributions of the various factors, we incorporated our results into the two-dimensional volatility basis set (2D-VBS). Our results show that the factors cover a broad spectrum of volatilities with no direct link between the average volatility and average O : C of the OA components. Agreement between our findings and previous publications is encouraging for our understanding of the evolution of atmospheric OA.

Hydrogen cyanide polymers, comets and the origin of life.

PubMed

Matthews, Clifford N; Minard, Robert D

2006-01-01

Hydrogen cyanide polymers--heterogeneous solids ranging in colour from yellow to orange to brown to black--could be major components of the dark matter observed on many bodies of the outer solar system including asteroids, moons, planets and, especially, comets. The presence on cometary nuclei of frozen volatiles such as methane, ammonia and water subjected to high energy sources makes them attractive sites for the ready formation and condensed-phase polymerization of hydrogen cyanide. This could account for the dark crust observed on Comet Halley in 1986 by the Vega and Giotto missions. Dust emanating from its nucleus would arise partly from HCN polymers as suggested by the Giotto detection of free hydrogen cyanide, CN radicals, solid particles consisting only of H, C and N, or only of H, C, N, O, and nitrogen-containing organic compounds. Further evidence for cometary HCN polymers could be expected from in situ analysis of the ejected material from Comet Tempel 1 after collision with the impactor probe from the two-stage Deep Impact mission on July 4, 2005. Even more revealing will be actual samples of dust collected from the coma of Comet Wild 2 by the Stardust mission, due to return to Earth in January 2006 for analyses which we have predicted will detect these polymers and related compounds. In situ results have already shown that nitriles and polymers of hydrogen cyanide are probable components of the cometary dust that struck the Cometary and Interstellar Dust Analyzer of the Stardust spacecraft as it approached Comet Wild 2 on January 2, 2004. Preliminary evidence (January 2005) obtained by the Huygens probe of the ongoing Cassini-Huygens mission to Saturn and its satellites indicates the presence of nitrogen-containing organic compounds in the refractory organic cores of the aerosols that give rise to the orange haze high in the atmosphere of Titan, Saturn's largest moon. Our continuing investigations suggest that HCN polymers are basically of two types: ladder structures with conjugated -C=N- bonds and polyamidines readily converted by water to polypeptides. Thermochemolysis GC-MS studies show that cleavage products of the polymer include alpha-amino acids, nitrogen heterocycles such as purines and pyrimidines, and provide evidence for peptide linkages. Hydrogen cyanide polymers are a plausible link between cosmochemistry and the origin of informational macromolecules. Implications for prebiotic chemistry are profound. Following persistent bolide bombardment, primitive Earth may have been covered by water and carbonaceous compounds, particularly HCN polymers which would have supplied essential components for establishing protein/nucleic acid life.

Synthesis and solution aggregation studies of a suite of mixed neutral and zwitterionic chromophores for second-order nonlinear optics.

PubMed

Peddie, Victoria; Anderson, Jack; Harvey, Joanne E; Smith, Gerald J; Kay, Andrew

2014-11-07

We report details of the synthesis of a series of bi- and trichromophores. These compounds contain mixtures of chromophores that have zwitterionic (ZWI) and neutral ground state (NGS) components covalently attached to each other. The neutral ground state moieties are based on dyes with aniline donors--such as Disperse Red 1--whereas the zwitterionic components are derived from chromophores with pro-aromatic donors such as 1,4-dihydropyridinylidene. By combining both ZWI and NGS components, we aim to develop novel compounds for nonlinear optics in which there is an enhancement of the overall hyperpolarizability coupled with a decrease in the net dipole moment. Thus, this approach should eliminate the electrostatic effects that result when only one type of chromophore is used, and so reduce the likelihood of undesirable aggregation occurring. This, in turn, should enable us to realize organic materials with large macroscopic optical nonlinearities. An analysis of the UV-vis results suggests that there is a strong dependence on solvent polarity that determines whether the embedded constituents should be treated as discrete elements; in low polarity solvents, there appear to be strong intramolecular interactions occurring, particularly when a 1,4-quinolinylidene-based donor is used in the ZWI component.

Chemical Composition and Potential Environmental Impacts of Water-Soluble Polar Crude Oil Components Inferred from ESI FT-ICR MS

PubMed Central

Liu, Yina; Kujawinski, Elizabeth B.

2015-01-01

Polar petroleum components enter marine environments through oil spills and natural seepages each year. Lately, they are receiving increased attention due to their potential toxicity to marine organisms and persistence in the environment. We conducted a laboratory experiment and employed state-of-the-art Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) to characterize the polar petroleum components within two operationally-defined seawater fractions: the water-soluble fraction (WSF), which includes only water-soluble molecules, and the water-accommodated fraction (WAF), which includes WSF and microscopic oil droplets. Our results show that compounds with higher heteroatom (N, S, O) to carbon ratios (NSO:C) than the parent oil were selectively partitioned into seawater in both fractions, reflecting the influence of polarity on aqueous solubility. WAF and WSF were compositionally distinct, with unique distributions of compounds across a range of hydrophobicity. These compositional differences will likely result in disparate impacts on environmental health and organismal toxicity, and thus highlight the need to distinguish between these often-interchangeable terminologies in toxicology studies. We use an empirical model to estimate hydrophobicity character for individual molecules within these complex mixtures and provide an estimate of the potential environmental impacts of different crude oil components. PMID:26327219