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Binding energies for the complexes of the S12L database by Grimme [Chem. Eur. J. 18, 9955 (2012)] were calculated using intermolecular symmetry-adapted perturbation theory combined with a density-functional theory description of the interacting molecules. The individual interaction energy decompositions revealed no particular change in the stabilisation pattern as compared to smaller dimer systems at equilibrium structures. This demonstrates that, to some extent, the qualitative description of the interaction of small dimer systems may be extrapolated to larger systems, a method that is widely used in force-fields in which the total interaction energy is decomposed into atomatom contributions. A comparison of the binding energies with accurate experimental reference values from Grimme, the latter including thermodynamic corrections from semiempirical calculations, has shown a fairly good agreement to within the error range of the reference binding energies. [ABSTRACT FROM AUTHOR]

A detailed analysis of photoluminescence (PL) from InP quantum dots (QDs) grown on Si has been carried out to understand the effect of substrate/host material in the luminescence and carrier escape process from the surface quantum dots. Such studies are required for the development of monolithically integrated next generation III-V QD based optoelectronics with fully developed Si microelectronics. The samples were grown by atmospheric pressure metalorganic chemical vapor deposition technique, and the PL measurements were made in the temperature range 10-80K. The distribution of the dot diameter as well as the dot height has been investigated from atomic force microscopy. The origin of the photoluminescence has been explained theoretically. The band alignment of InP/Si heterostructure has been determined, and it is found be type II in nature. The positions of the conduction band minimum of Si and the 1st excited state in the conduction band of InP QDs have been estimated to understand the carrier escape phenomenon. A blue shift with a temperature co-efficient of 0.19meV/K of the PL emission peak has been found as a result of competitive effect of different physical processes like quantum confinement, strain, and surface states. The corresponding effect of blue shift by quantum confinement and strain as well as the red shift by the surface states in the PL peaks has been studied. The origin of the luminescence in this heterojunction is found to be due to the recombination of free excitons, bound excitons, and a transition from the 1st electron excited state in the conduction band (e1) to the heavy hole band (hh1). Monotonic decrease in the PL intensity due to increase of thermally escaped carriers with temperature has been observed. The change in barrier height by the photogenerated electric-field enhanced the capture of the carriers by the surface states rather than their accumulation in the QD excited state. From an analysis of the dependence of the PL intensity, peak position, and line width with temperature and excitation source, the existence of free and bound excitonic recombination together with e1 →hh1 transitions in the QDs is established. [ABSTRACT FROM AUTHOR]

We bring together solid state 1H spin-lattice relaxation rate measurements, scanning electron microscopy, single crystal X-ray diffraction, and electronic structure calculations for two methyl substituted organic compounds to investigate methyl group (CH3) rotational dynamics in the solid state. Methyl group rotational barrier heights are computed using electronic structure calculations, both in isolated molecules and in molecular clusters mimicking a perfect single crystal environment. The calculations are performed on suitable clusters built from the X-ray diffraction studies. These calculations allow for an estimate of the intramolecular and the intermolecular contributions to the barrier heights. The 1H relaxation measurements, on the other hand, are performed with polycrystalline samples which have been investigated with scanning electron microscopy. The 1H relaxation measurements are best fitted with a distribution of activation energies for methyl group rotation and we propose, based on the scanning electron microscopy images, that this distribution arises from molecules near crystallite surfaces or near other crystal imperfections (vacancies, dislocations, etc.). An activation energy characterizing this distribution is compared with a barrier height determined from the electronic structure calculations and a consistent model for methyl group rotation is developed. The compounds are 1,6-dimethylphenanthrene and 1,8-dimethylphenanthrene and the methyl group barriers being discussed and compared are in the 2-12 kJ mol-1 range. [ABSTRACT FROM AUTHOR]

The transition voltage of three different asymmetric Au/poly(phenylene) thiol/Au molecular junctions in which the central molecule is either benzene thiol, biphenyl thiol, or terphenyl thiol is investigated by first-principles quantum transport simulations. For all the junctions, the calculated transition voltage at positive polarity is in quantitative agreement with the experimental values and shows weak dependence on alterations of the Au-phenyl contact. When compared to the strong coupling at the Au-S contact, which dominates the alignment of various molecular orbitals with respect to the electrode Fermi level, the coupling at the Au-phenyl contact produces only a weak perturbation. Therefore, variations of the Au-phenyl contact can only have a minor influence on the transition voltage. These findings not only provide an explanation to the uniformity in the transition voltages found for π-conjugated molecules measured with different experimental methods, but also demonstrate the advantage of transition voltage spectroscopy as a tool for determining the positions of molecular levels in molecular devices. [ABSTRACT FROM AUTHOR]

Acridine orange (AO), a biosensitive molecule that is customarily used for labeling nucleic acids including DNA and RNA, is here investigated as a cost effective, water soluble, and photoactive material for the fabrication of potentially biosensitive organic photovoltaics. The electronic energy levels of AO are determined using Kelvin Probe Force Microscopy (KPFM) and UV-Visible spectroscopy. The effect of anticrystallization agents, as well as low-temperature annealing, on the work function of AO is investigated: amorphous AO films are shown to possess a significantly higher work function than microcrystalline AO films and the work function also increases by annealing. Photo-induced processes in AO films are investigated by considering the changes of the KPFM signal under illumination. We demonstrate that acridine orange is able to photogenerate electron-hole pairs at rates comparable to the most commonly used solar-grade photovoltaic materials, including polythiophenes. In addition, the effect of the morphology of different types of AO thin films spun from different solvents is studied in bilayer photovoltaic devices fabricated from stacks of AO and phenyl-C61-butyric acid methyl ester thin films. [ABSTRACT FROM AUTHOR]

The possibility of the fabrication of organic devices suitable to be applied in bio-sensing fields depends largely on the availability of organic compounds displaying robust electrical properties even in aqueous solutions and effective biocompatibility features. In this paper, we report about the good cellular biocompatibility and the electrical response stability in an ionic medium of n-type organic transistors based on the recently developed PDI-8CN2 oligomer. The biocompatibility has been tested by analyzing the adhesion and viability of two different cell lines, human epithelial HeLa cells and murine neuronal F11 cells, on PDI-8CN2 films grown by organic molecular beam deposition (OMBD) on SiO2 substrates. The effect of film thickness on cell attachment was also tested. Uncoated SiO2 substrates were used as control surfaces and sexithiophene (T6) as device testing control. Moreover, the possible toxicity of -CN groups of PDI-8CN2 was tested on HeLa cell cultures, using PDI-8 and T6 molecules as controls. Results showed that, although at high concentration these organic compounds are toxic in solution, if they are presented in form of film, cell lines can attach and grow on them. The electrical response stability of PDI-8CN2 transistors in a cellular culture medium characterized by high concentrations of ionic species has been also investigated. For this purpose, low-voltage operation devices with VGS ranging from -5 V to 5 V, able to strongly reduce the influence of Faradaic currents coming from the electrical operation in an highly ionic environment, have been fabricated on 35 nm thick SiO2 layers and electrically characterized. These results are useful to experimentally define the main critical issues to be further addressed for the fabrication of reliable bio-sensors based on organic transistors. [ABSTRACT FROM AUTHOR]

In this paper, we report on electronic transport and impedance measurements on thin films of unintentionally hole doped 3,6-dipyrenyl-N-hexylcarbazole. Evidence for doping from dc conductivity, ESR, and capacitance measurements is presented. From a study of the bias, temperature and frequency dependence of capacitance, we estimate the integrated density of states above the Fermi level to be 1017/cm3. This is also the doping concentration in these samples. [ABSTRACT FROM AUTHOR]

Levan has various potential applications in the pharmaceutical and food industries, such as cholesterol-lowering agents and prebiotics, due to its beneficial properties, which depend on its length and branching degree. A previous study also found that the branching degree of levan affected anti-tumor activities against SNU-1 and HepG2 tumor cell lines. Despite its promising potential, the properties of levans with different branching degrees are not well understood at the molecular level. In two models of the generalized Born implicit solvent (GBHCT and GBOBC1), we employed replica-exchange molecular dynamics simulations to explore conformational spaces of 34-residue levans (L34) with branching degrees of zero (LFO34B0), one (LFO34B1), three (LFO34B3) and five (LFO34B5), as well as to elucidate their structural and molecular properties. To ensure a fair comparison of the effects of branching degree on these properties, we focused on analyzing the properties of the central 21-residue of the main chains of all systems. Our results show that all major representative conformations tend to form helix-like structures with kinks, where two-kink helix-like structures have the highest population. As branching degree increases, the population of helix-like structures with zero or one kink tends to increase slightly. As the number of kinks in the structures with the same branching degree increases, the average values of the lengths and angles among centers of masses of three consecutive turns of residue i, i+3, and i+6 tended to decrease. Due to its highest occurring frequencies, the O6 (i)—H3O (i+1) hydrogen bond could be important for helix-like structure formation. Moreover, hydrogen bonds forming among the branching residue (br), branching position (bp) and other residues of L34B1, L34B3 and L34B5 were identified. The O1(bp)—H3O(br), O1(br)—H3O(br) and O5(br)—H1O(br) hydrogen bonds were found in the first-, second- and third-highest occurrence frequencies, respectively. Our study provides novel and important insights into conformational spaces and the structural and molecular properties of 34-residue levans with various branching degrees, which tend to form helix-like structures with kinks. [ABSTRACT FROM AUTHOR]

The Fourier transform infrared (FTIR) spectra of organic compounds 4-fluoro-2-azido-1-phenylethanone (FAP), 4-chloro-2-azido-1-phenylethanone (CAP) and 4-bromo-2-azido-1-phenylethanone (BAP) have been recorded in the region 4000-400 cm −1 . The optimized molecular structure for global minimum energy of the titled molecules is determined by evaluating torsional potentials as a function of rotation angle about free rotation bonds among the substituent groups subjecting them to DFT employing B3LYP functional with 6–311++G (d,p) basis set. The vibrational frequencies along with infrared intensities are computed by SQM procedure. The rms error between observed and calculated frequencies is found to be 9.27, 8.17 and 7.95 cm −1 for FAP, CAP and BAP, respectively which shows good agreement between experimental and scaled values of calculated frequencies obtained by DFT. The vibrational assignments of all the fundamental bands of each molecule are made unambiguously using PED and eigen vectors obtained in the computations. The computed values of dipole moment, polarizability and hyperpolarizability indicate that the titled molecules exhibit NLO behaviour and hence may be considered for potential applicants for the development of NLO materials. HOMO and LUMO energies evaluated in the study demonstrate chemical stability of the molecules. NBO analysis is made to study the stability of the molecules arising from hyper conjugative interactions and charge delocalization. The molecular electrostatic surface potential (MESP) and thermodynamic parameters are also evaluated. [ABSTRACT FROM AUTHOR]

This study developed a novel method to promote the remediation efficiency of air sparging. According to the enhanced-volatilization theory presented in this study, selected alcohols added to groundwater can highly enhance the volatilization amounts of organic compounds with high Henry’s law constants. In this study, the target organic compounds consisted of n -hexane, n -heptane, benzene, toluene, 1,1,2-trichloroethane, and tetrachloroethene. n -pentanol, n -hexanol, and n -heptanol were used to examine the changes in the volatilization amounts of organic compounds in the given period. Two types of soils with high and low organic matter were applied to evaluate the transport of organic compounds in the soil–water system. The volatilization amounts of the organic compounds increased with increasing alcohol concentrations. The volatilization amounts of the test organic compounds exhibited a decreasing order: n -heptanol > n -hexanol > n -pentanol. When 10 mg/L n -heptanol was added to the system, the maximum volatilization enhancement rate was 18-fold higher than that in distilled water. Samples of soil with high organic matter might reduce the volatilization amounts by a factor of 5–10. In the present study, the optimal removal efficiency for aromatic compounds was approximately 98%. [ABSTRACT FROM AUTHOR]

An increase in air temperature related to climate change results in the retreat of glaciers, the degradation of permafrost, and the expansion of glacier-free areas in the polar regions. All these processes lead to changes in the Arctic landscape. They influence the hydrochemistry of streams and rivers fed by glaciers and thawing permafrost. In this study, we examine eighty two water samples from two non-glaciated catchments with snow-permafrost regime: the Tyvjobekken Creek and the Reindeer Creek (NW Wedel-Jarlsberg Land, Spitsbergen). We cover hydrometeorological measurements, fluctuations of physicochemical parameters (pH, specific electrolytic conductivity (SEC)), and the presence of selected organic compounds (dissolved organic carbon (DOC), formaldehyde (HCHO), ∑ phenols). The obtained levels of DOC (0.061–0.569 mg C L − 1 ) and HCHO (< LOD-0.140 mg L − 1 ) in water samples of these two high Arctic creeks confirm the role of the melting permafrost as a rich source of terrestrial organic carbon and organic pollutants, as well as the impact of rainfall on surface water chemistry. It was found that fluctuations of physicochemical indices (pH, SEC, DOC) were related to changes in mean daily discharge of Reindeer Creek (0.012–0.034 m 3 s − 1 ) and Tyvjobekken Creek (0.011–0.015 m 3 s − 1 ) (r > 0.40). The Tyvjobekken Creek catchment, in contrast to Reindeer Creek catchment, turned out to be resistant to rapid changes in meteorological conditions (r < 0.10) and surface runoff. The processes of permafrost thawing, calcium carbonate dissolution, and biogeochemical “breathing” of soils proved to be crucial for the development of water chemistry. In conclusion, the surface water chemistry of the Reindeer Creek was found to result from the mutual influence of hydrometeorological indices and the biogeochemical environment of the catchment. [ABSTRACT FROM AUTHOR]

Autoignition temperature (AIT) is one of the most important safety specifications used to characterize the hazard potentials of a chemical substance. A simple model is introduced for reliable prediction of the AIT oforganic compounds containing energetic functional groups nitro, nitrate, nitramine and peroxide. It requires the only molecular structure oforganic energetic compounds without using complex molecular descriptors and computer codes where they need expert users. Model building has been constructed on the basis of the measured AIT of 45 organic energetic compounds and compared with the predicted results of the best available group additivity method. For 9 compounds with unlike and complex molecular structures, the new model has also been checked that gives good predictions. The root mean square (RMS) deviations of the new model and group additivity method are 47.45 and 194.25 K, respectively, for 54 compounds (corresponding to 111 data points). [ABSTRACT FROM AUTHOR]

Rotating biological filter (RBF), which provides higher oxygen mass transfer has been developed for treating gaseous volatile organic compounds (VOCs) such as BTEX (Benzene, toluene, ethylbenzene and xylene) at higher concentrations. The screening of enriched cultures has been done initially to enhance the performance of RBF for treating xylene, toluene and xylene, and BTEX at various loading rates. The removal efficiency of BTEX was maximum (82%), higher than toluene and xylene (79%), and xylene (72%). The presence of xylene enhanced the removal of toluene in the mixture. In the BTEX, toluene was found to be highly biodegradable followed by ethylbenzene, benzene and xylene. The RBF also removed nutrients from wastewater along with VOCs. The stability study of RBF showed that supply of nutrient media influenced the RBF performance more. Further, the predominant strain identified in the mixed culture was Enterobacter cloacae SP4001, responsible for biodegradation of BTEX. [ABSTRACT FROM AUTHOR]

Mycelium of ectomycorrhizal fungi colonizes soil that is extremely heterogeneous in terms of spatial arrangement as well as chemical and biological properties. Here we addressed which of the soil components would have the greatest influence on hyphal development of an ectomycorrhizal fungus, the summer truffle ( Tuber aestivum ). We tested a range of inorganic and organic compounds and bacterial strains isolated from truffle mycorrhizosphere, added to truffle grounds in small compartments accessible exclusively to the hyphae and not to host plant roots. Our results showed stimulation of truffle hyphal growth by high dosis of lime powder, whereas leaf litter had no effect. Further, we recorded significant stimulation of the hyphal growth by several organic compounds (gallic acid, cellulose and calcium formate), whereas no significant stimulation was observed by any of the inorganic compounds or bacterial cultures mixed with an inert carrier. None of the amendments, however, sustained the truffle growth rate recorded in unsterile field soil. These results indicate that the development of hyphae of T. aestivum in soil may well require complex and micro-heterogeneous environment, where specific organic compounds and calcium carbonate play particularly important roles. [ABSTRACT FROM AUTHOR]

A positive matrix factorization model (US EPA PMF version 5.0) was applied for the source apportionment of the dataset of 37 non-methane volatile organic compounds (NMVOCs) measured from 19 December 2012 to 30 January 2013 during the SusKat-ABC international air pollution measurement campaign using a proton-transfer-reaction time-of-flight mass spectrometer in the Kathmandu Valley. In all, eight source categories were identified with the PMF model using the new constrained model operation mode. Unresolved industrial emissions and traffic source factors were the major contributors to the total measured NMVOC mass loading (17.9 and 16.8 %, respectively) followed by mixed industrial emissions (14.0 %), while the remainder of the source was split approximately evenly between residential biofuel use and waste disposal (10.9 %), solvent evaporation (10.8 %), biomass co-fired brick kilns (10.4 %), biogenic emissions (10.0 %) and mixed daytime factor (9.2 %). Conditional probability function (CPF) analyses were performed to identify the physical locations associated with different sources. Source contributions to individual NMVOCs showed that biomass co-fired brick kilns significantly contribute to the elevated concentrations of several health relevant NMVOCs such as benzene. Despite the highly polluted conditions, biogenic emissions had the largest contribution (24.2 %) to the total daytime ozone production potential, even in winter, followed by solvent evaporation (20.2 %), traffic (15.0 %) and unresolved industrial emissions (14.3 %). Secondary organic aerosol (SOA) production had approximately equal contributions from biomass co-fired brick kilns (28.9 %) and traffic (28.2 %). Comparison of PMF results based on the in situ data versus REAS v2.1 and EDGAR v4.2 emission inventories showed that both the inventories underestimate the contribution of traffic and do not take the contribution of brick kilns into account. In addition, the REAS inventory overestimates the contribution of residential biofuel use and underestimates the contribution of solvent use and industrial sources in the Kathmandu Valley. The quantitative source apportionment of major NMVOC sources in the Kathmandu Valley based on this study will aid in improving hitherto largely un-validated bottom-up NMVOC emission inventories, enabling more focused mitigation measures and improved parameterizations in chemical transport models. [ABSTRACT FROM AUTHOR]

Drilling cuttings and drilling mud samples were collected from Zarama 10 and Zarama 11 oil wells in the Niger Delta at various depths in order to characterize the extractable organic matter and biomarkers distribution patterns. The total organic carbon contents of the samples were determined using Walkley Black method. The distribution ofn-alkanes, pristane, phytane, phenanthrene, and its alkylated derivatives were studied by gas chromatography-mass spectrometry. The total organic carbon values show that the samples satisfy the minimum amount of 0.5 wt% organic matter required to serve as a potential source-rock of petroleum. The distribution ofn-alkanes and alkylated phenanthrenes shows that the samples contain admixture (marine and terrestrial) of organic matter. The pristane/phytane ratio (1.25–2.25) indicates sub-oxic depositional environment for the organic matter of the samples. Equivalent vitrinile reflectance values calculated from methyl phenanthrene index (MPI-1) were in the range of 1.23–1.38% for the well studied. The maturity parameters obtained were used to assess maturity, which revealed high maturity level of the two wells. Further, calculated vitrinite reflectance (Rc) confirmed that the sediments have a range of maturity within the “oil window.” [ABSTRACT FROM PUBLISHER]

The article presents a study on macromolecular organic matter in samples from asteroid (162173) Ryugu shows that its organic matter consists of primordial materials modified by aqueous alteration on the asteroid's parent body. It mentions that the organic matter consists of aromatic and aliphatic carbons, ketones, and carboxyls, with functional group compositions consistent with those of insoluble organic matter from primitive carbonaceous chondritic meteorites macromolecular diversity.

Returning samples from Mars will require an effective method to assess and select the highest-priority geological materials. The ideal instrument for sample triage would be simple in operation, limited in its demand for resources, and rich in produced diagnostic information. Pyrolysis-Fourier infrared spectroscopy (pyrolysis-FTIR) is a potentially attractive triage instrument that considers both the past habitability of the sample depositional environment and the presence of organic matter that may reflect actual habitation. An important consideration for triage protocols is the sensitivity of the instrumental method. Experimental data indicate pyrolysis-FTIR sensitivities for organic matter at the tens of parts per million level. The mineral matrix in which the organic matter is hosted also has an influence on organic detection. To provide an insight into matrix effects, we mixed well-characterized organic matter with a variety of dry minerals, to represent the various inorganic matrices of Mars samples, prior to analysis. During pyrolysis-FTIR, serpentinites analogous to those on Mars indicative of the Phyllocian Era led to no negative effects on organic matter detection; sulfates analogous to those of the Theiikian Era led, in some instances, to the combustion of organic matter; and palagonites, which may represent samples from the Siderikian Era, led, in some instances, to the chlorination of organic matter. Any negative consequences brought about by these mineral effects can be mitigated by the correct choice of thermal extraction temperature. Our results offer an improved understanding of how pyrolysis-FTIR can perform during sample triage on Mars. Key Words: Mars-Life-detection instruments-Search for Mars' organics-Biosignatures. Astrobiology 16, 831-845. [ABSTRACT FROM AUTHOR]

Ecosystem metabolism determines organic matter cycling and trophic structure in aquatic ecosystems. Ecosystem metabolism is well studied in ponds, lakes, estuaries, streams, and rivers, but it is seldom investigated in large reservoirs. Here, we report daily ecosystem metabolism (26 January-10 May 2009), measured with the free-water technique, in the surface layer of Xiangxi Bay, Three Gorges Reservoir. Further, we investigated the potential factors influencing variation in metabolic processes by systematically testing 4 hypotheses based on phytoplankton biomass, water temperature, nutrient concentration, and light availability. Daily dynamics of respiration (R), gross primary production (GPP), and net ecosystem production (NEP) had high variability during the spring phytoplankton blooms in Xiangxi Bay. GPP ranged from 0.57 to 9.79 mg O2 L-1 d-1; R ranged from 0.27 to 7.80 mg O2 L-1 d-1; and NEP ranged from -4.24 to 1.96 mg O2 L-1 d-1 (mean ? -0.26 mg O2 L-1 d-1). Further analysis showed that: 1) GPP is determined by phytoplankton biomass and maximum daily photosynthetically active radiation (PAR); 2) R is determined by phytoplankton biomass and water temperature; and 3) NEP has a significant positive correlation with soluble reactive P. However, the potential mechanism explaining the relationship between NEP and P requires further research. Our study reveals that the metabolic processes in Xiangxi Bay are determined mainly by phytoplankton biomass, water temperature, and maximum daily PAR. This work improves our understanding of ecosystem metabolism in Three Gorges Reservoir. [ABSTRACT FROM AUTHOR]

Interaction of viruses and cells has tremendous impact on cellular and viral evolution, nutrient cycling and decay of organic matter. Thus, viruses can indirectly affect complex processes such as climate change and microbial pathogenicity. During recent decades, studies on extreme environments have introduced us to archaeal viruses and viruses infecting extremophilic bacteria or eukaryotes. Hypersaline environments are known to contain strikingly high numbers of viruses (~109 particles per ml). Halophilic archaea, bacteria and eukaryotes inhabiting hypersaline environments have only a few cellular predators, indicating that the role of viruses is highly important in these ecosystems. Viruses thriving in high salt are called haloviruses and to date more than 100 such viruses have been described. Virulent, temperate, and persistent halovirus life cycles have been observed among the known isolates including the recently described SNJ1-SNJ2 temperate virus pair which is the first example of an interplay between two haloviruses in one host cell. In addition to direct virus and cell isolations, metagenomics have provided a wealth of information about virus-host dynamics in hypersaline environments suggesting that halovirus populations and halophilic microorganisms are dynamic over time and spatially distributed around the highly saline environments on the Earth. [ABSTRACT FROM AUTHOR]

We designed a stereodynamic system, where the chirality of the analyte serves as a template for the helicity of the first coordination sphere of Co(ii). Giant VCD bands induced by Co(ii) allow the measurement of a completely significant and conclusive VCD spectrum in only a few seconds and/or on minute quantities of the analyte. This paves the way for the development of similar protocols, overcoming the limitations due to weak VCD signals for the assignment of absolute configurations. [ABSTRACT FROM AUTHOR]

This work involves the study of the influence of textural and chemical adsorbent properties on natural organic matter (NOM) removal and the simultaneous adsorption of caffeine and NOM in pharmaceutical wastewater. The performance of a microporous activated carbon, Calgon F400, a synthesized mesoporous carbon from peach stones and a commercial sepiolite in the removal of NOM of a WWTP effluent, and the competitive adsorption of caffeine/NOM were evaluated. It was evidenced that the microporous structure of the adsorbents significantly conditioned the removal of NOM, finding that F400 activated carbon (microporous volume of 0.46 cm3 g−1) led to a NOM removal of 45%. The presence of NOM in the aqueous medium led to worse adsorption parameters, including adsorption capacity at breakthrough time, mass transfer zone length and fractional bed utilization. Additionally, anovershootingin the Total Organic Carbon concentration (TOC/TOC0 = 1.05) was observed in the sepiolite adsorption fixed-bed experiment, due to the displacement of the background NOM. The tested adsorbents were efficient in the removal of caffeine from a pharmaceutical wastewater, finding a competitive effect between the target compound and the background NOM for the active sites. [ABSTRACT FROM PUBLISHER]

Within the repertoire of organic chemical transformations, the halogenation of substrates is among the most versatile, reliable, and broadly applicable reactions. Although a multitude of different methods are known today, there is still a huge demand for novel and, in particular, catalytic halogenation methods that exhibit new reactivities and selectivities. The class of hypervalent iodanes meets exactly these needs and thus offers a great opportunity to fuel this highly desirable direction within the field of halogenation chemistry. This Concept gives a short overview of recent examples focusing on selective and/or mechanistically unusual halogenations. [ABSTRACT FROM AUTHOR]

We have investigated the electrochemically triggered cycloreversion of quadricyclane (QC) to norbornadiene (NBD), a system that holds the potential to combine both energy storage and conversion in a single molecule. Unambiguous voltammetric traces are obtained for pure NBD and pure QC, the latter a strained polycyclic isomer of the former. The difference in redox potentials is smaller than the energy difference between the neutral molecules. This is owing to a significant energy difference between the corresponding radical cations, as demonstrated by density functional theory (DFT) calculations. The vibrational modes of each pure compound are characterized experimentally in the fingerprint region and identified by DFT methods. Thermal and electrochemical transformations of NBD and QC are monitored in situ by IR spectroelectrochemical methods. The kinetics of the cycloreversion of QC to NBD, which is catalyzed by oxidizing equivalents, can be controlled by an applied electrode potential, which implies the ability to adjust in real time the release of thermal power stored in QC. [ABSTRACT FROM AUTHOR]

The purpose of this work was to explore the application of low frequency ultrasound for the desorption of 4-chlorophenol (4-CP) from saturated granular activated carbon (GAC) in a continuous flow ultrasonic reactor. The effects of operating parameters such as the amount of adsorbent, intensity of ultrasound irradiation, temperature, flow rate of desorbing solution, NaOH, ethyl alcohol, and mixture of NaOH and ethyl alcohol on the desorption process were investigated. The obtained results show that the desorption decreased with increasing the amount of adsorbent and intensity of ultrasound irradiation. The amount of 4-CP desorption gradually increased with the increase in temperature and flow rate of desorbing solution. Using NaOH or/and ethyl alcohol as desorbing solutions causes an enhancement of the desorption. Desorption was improved with increasing the concentration of NaOH and ethyl alcohol in the desorbing solution. Future studies should innovate the ultrasound-assisted desorption process in a pilot-scale test that applies this desorption procedure to a GAC adsorber used in organic compounds removal. [ABSTRACT FROM PUBLISHER]

The search for indisputable traces of life in Archean cherts is of prime importance. However, their great age and metamorphic history pose constraints on the study of molecular biomarkers. We propose a quantitative criterion to document the thermal maturity of organic matter in rocks in general, and Archean rocks in particular. This is definitively required to select the best candidates for seeking non-altered sample remnants of life. Analysis of chemical (Raman spectroscopy, 13C NMR, elemental analysis) and structural (HRTEM) features of Archean and non-Archean carbonaceous matter (CM) that was submitted to metamorphic grades lower than, or equal to, that of greenschist facies showed that these features had all undergone carbonization but not graphitization. Raman-derived quantitative parameters from the present study and from literature spectra, namely, R1 ratio and FWHM-D1, were used to draw a carbonization continuum diagram showing two carbonization stages. While non-Archean samples can be seen to dominate the first stage, the second stage mostly consists of the Archean samples. In this diagram, some Archean samples fall at the boundary with non-Archean samples, which thus demonstrates a low degree of carbonization when compared to most Archean CM. As a result, these samples constitute candidates that may contain preserved molecular signatures of Archean CM. Therefore, with regard to the search for the oldest molecular traces of life on Earth, we propose the use of this carbonization continuum diagram to select the Archean CM samples. Key Words: Archean--Early life--Kerogen--Raman spectroscopy--Carbonization. Astrobiology 16, 407-417. [ABSTRACT FROM AUTHOR]

The element contents and organic matter-element relation between Lias-aged coals exposed in four fields in Gümüşhane and Bayburt were investigated. In general, fixed carbon and gross calorific values of the Edire and Balkaynak coals are higher than Güvercinlik and Çerçi coals. The highest ash yields were observed in the Çerçi coals. The concentrations of Mg, P, Ca, Mo, Y, Ni, U, Zn, Ga, Ba, W, Sr, Ta, and Be of the analysed coals are positively correlated with ash yield, indicating an organic affinity. The Lias-aged coals located in Gümüşhane and Bayburt are low-rank coals. [ABSTRACT FROM PUBLISHER]

Electron-deficient enamines such as enaminones and enaminoesters are moieties showing widespread application in organic synthesis. Among the various available electron-deficient enamines, the N, N-disubstituted amino-functionalized ones (tertiary enamines) represent a class of special enamines with distinct properties and important applications. Based on our longstanding interest in exploring novel synthetic methods using electron-deficient tertiary enamines, we present herein the research advances in organic synthesis via domino reactions making use of the combinatorial C-N, C=C, C-H, and other bond transformations of electron-deficient tertiary enamines. [ABSTRACT FROM AUTHOR]

A new approach to prepare heterometallic cluster organic frameworks has been developed. The method was employed to link Anderson-type polyoxometalate (POM) clusters and transition-metal clusters by using a designed rigid tris(alkoxo) ligand containing a pyridyl group to form a three-fold interpenetrated anionic diamondoid structure and a 2D anionic layer, respectively. This technique facilitates the integration of the unique inherent properties of Anderson-type POM clusters and cuprous iodide clusters into one cluster organic framework. [ABSTRACT FROM AUTHOR]

Background: Phenol is one of the most versatile and important organic compound. It is also a growing concern as water pollutants due to its high persistence and toxicity. Removal of Phenol from wastewaters was investigated using a novel nanoparticle adsorption and nanofiltration technique named as Nanoparticle Assisted Nano Filtration (NANF). Methods: The nanoparticle used for NANF study were silver nanoparticles and synthesized to three distinct average particle sizes of 10 nm, 40 nm and 70 nm. The effect of nanoparticle size, their concentrations and their tri and diparticle combinations upon phenol removal were studied. Results: Total surface areas (TSA) for various particle size and concentrations have been calculated and the highest was 4710 x 1012 nm² for 10 nm particles and 180 ppm concentration while the lowest was for 2461 x 1011 for 70 nm and 60 ppm concentrations. Tri and diparticle studies showed more phenol removal % than that of their individual particles, particularly for using small particles on large membrane pore size and large particles at low concentrations. These results have also been confirmed with COD and toxicity removal studies. Conclusions: The combination of nanoparticles adsorption and nanofiltration results in high phenol removal and mineralization, leading to the conclusion that NANF has very high potential for treating toxic chemical wastewaters. [ABSTRACT FROM AUTHOR]

Geminal bis- and tristriazoles belong to a rare and mainly overlooked class of organic compounds with interesting properties. This review summarizes the methods for their preparation. Moreover, applications of these compounds are described, ranging from ring extensions to their use as reactive intermediates for the efficient construction of heterocycles. 1 Introduction 2 Bistriazoles 2.1 Bistriazoles (Tetrahedral Carbon) 2.2 Bistriazoles (Trigonal Carbon) 3 Tristriazoles 4 Conclusion and Prospectives [ABSTRACT FROM AUTHOR]

Chemical treatment processes have mostly been considered as an efficient way for biosolid minimization. The improvement of sludge dewatering was more a welcome side-effect of these sequential processes. In this study, heat-activated sodium peroxydisulphate (PDS) and potassium peroxymonosulphate (MPS) were applied in order to disintegrate waste activated sludge (WAS). PDS and MPS treatment of WAS results in the polymer transfer of organic matter from the solid phase to the liquid phase. Our research work was done for chemical disintegration of WAS by PDS and MPS in doses of 0.2%, 0.4%, 0.6%, 0.8% and 1% (169.5, 339.0, 508.5, 678.0 and 847.5 mg ) activated at temperatures of 60°C and 90°C for 30 min. The application of these methods causes the soluble chemical oxygen demand value to increase in the supernatant. In addition, there was a positive influence on the sludge volume index which decreased for the highest doses of PDS of over 63% and 77% and MPS of over 78% and 82% through heat activation at temperatures of 60°C and 90°C, respectively. Furthermore, MPS was more successful in the floc particle destruction, therefore it caused a higher sludge settlement acceleration (sedimentation/compaction speed) than PDS. The experimental results demonstrated that the application of heat-activated PDS and MPS may become a novel effective way of processing sewage sludge. [ABSTRACT FROM PUBLISHER]

To improve methane adsorption by pore structure optimization, we developed a new organic linker and used it to construct a NbO-type metal–organic framework ZJNU-53 that, after activation, exhibits exceptionally high methane storage and working capacities of 241 and 190 cm3 (STP) cm−3 at 298 K and 65 bar, respectively, if the packing loss is not considered, which are among the highest reported for MOF materials. [ABSTRACT FROM AUTHOR]

The effect of precipitation regime on the C cycle of tropical forests is poorly understood, despite the existence of models that suggest a drier climate may substantially alter the source-sink function of these ecosystems. Along a precipitation regime gradient containing 12 mature seasonally dry tropical forests growing under otherwise similar conditions (similar annual temperature, rainfall seasonality, and geological substrate), we analyzed the influence of variation in annual precipitation (1240 to 642 mm) and duration of seasonal drought on soil C. We investigated litterfall, decomposition in the forest floor, and C storage in the mineral soil, and analyzed the dependence of these processes and pools on precipitation. Litterfall decreased slightly - about 10% - from stands with 1240 mm yr−1 to those with 642 mm yr−1, while the decomposition decreased by 56%. Reduced precipitation strongly affected C storage and basal respiration in the mineral soil. Higher soil C storage at the drier sites was also related to the higher chemical recalcitrance of litter (fine roots and forest floor) and the presence of charcoal across sites, suggesting an important indirect influence of climate on C sequestration. Basal respiration was controlled by the amount of recalcitrant organic matter in the mineral soil. We conclude that in these forest ecosystems, the long-term consequences of decreased precipitation would be an increase in organic layer and mineral soil C storage, mainly due to lower decomposition and higher chemical recalcitrance of organic matter, resulting from changes in litter composition and, likely also, wildfire patterns. This could turn these seasonally dry tropical forests into significant soil C sinks under the predicted longer drought periods if primary productivity is maintained. [ABSTRACT FROM AUTHOR]

A human in vivo metabolism study was carried out to investigate the impact of the trimethylselenium ion (TMSe) status on metabolism and toxicokinetics of sodium selenite and selenized yeast. Nine healthy human volunteers were orally exposed to 200 µg selenium as sodium selenite and seven with selenized yeast (100 µg selenium). In each intervention group, three subjects belong to TMSe eliminators. Blood samples were withdrawn before and up to 6 h after administration. Urine samples were collected before and within 24 h after administration. Total selenium (Se) was quantified in blood plasma and urine and low molecular Se species in urine. Selenium concentration in plasma increased from 84.5 ± 13.2 µg Se/L before to 97.4 ± 13.2 µg Se/L 2-3 h after selenite supplementation and 89.5 ± 12.9 µg Se/L to 92.1 ± 13.9 µg Se/L after selenized yeast intake. The oral ingestion caused an additional Se elimination via urine of 16.9 ± 10.6 µg/24 h (TMSe elim.: 10.8 ± 6.9 µg/24 h; non-TMSe elim.: 20.0 ± 11.3 µg Se/24 h) after selenite exposure and 11.8 ± 4.1 µg/24 h (TMSe elim.: 10.8 ± 4.6 µg/24 h; non-TMSe elim.: 12.6 ± 4.2 µg Se/24 h) after selenized yeast exposure. Methyl-2-acetamido-2-deoxy-1-seleno-β- d-galactopyranoside (SeSug1) was the main metabolite in all urine samples, whereas TMSe was another main metabolite in TMSe eliminators' urine. After selenite exposure, a small amount of the dose (0.5 ± 0.2 %) was oxidized to selenate and rapidly excreted via urine. With the exception of selenite exposure in TMSe eliminators, the comparison of total Se and the sum of quantified Se species revealed a high renal portion of unidentified species. The study indicated a different metabolism of inorganic and organic Se compounds in human, but also crucial differences of Se metabolism in TMSe eliminators and non-TMSe eliminators. [ABSTRACT FROM AUTHOR]

The objective of this experiment was to test the hypothesis that the apparent total tract digestibility (ATTD) of DM, OM, fiber, and GE by weanling pigs and the concentration of DE and ME in full-fat rice bran (FFRB), defatted rice bran (DFRB), brown rice, and broken rice is improved if microbial xylanase is added to the diet. Eighty pigs (13.6 ± 0.8 kg initial BW) were allotted to 10 diets with 8 replicate pigs per diet in a randomized complete block design with 2 blocks of 40 pigs. A basal diet based on corn and soybean meal and 4 diets containing corn, soybean meal, and each of the 4 rice coproducts were formulated. The rice coproducts and corn and soybean meal were the only sources of energy in the diets. Five additional diets that were similar to the initial 5 diets with the exception that they also contained 16,000 units of xylanase (Econase XT-25; AB Vista, Marlborough, UK) were also formulated. All diets also contained 1,500 units of microbial phytase (Quantum Blue 5G; AB Vista). The DE and ME and the ATTD of DM, OM, fiber, and GE in diets and ingredients were calculated using the direct method and the difference method, respectively. Results indicated that the concentrations of DE and ME (DM basis) in FFRB and DFRB increased (P < 0.05) if xylanase was used. Broken rice had a greater (P < 0.05) concentration of DE and ME than FFRB and DFRB if no xylanase was added to the diets, but if xylanase was used, no differences in ME among FFRB, brown rice, and broken rice were observed. The ATTD of DM was greater (P < 0.05) in ingredients with xylanase than in ingredients without xylanase and there was a tendency (P = 0.067) for the ATTD of OM to be greater if xylanase was used. The ATTD of NDF in FFRB was greater (P < 0.05) when xylanase was added than if no xylanase was used, whereas the ATTD of NDF in DFRB was not affected by the addition of xylanase. In conclusion, if no xylanase was used, broken rice and brown rice have greater concentrations of DE and ME than FFRB and DFRB, and these values were not increased by microbial xylanase. However, xylanase increased the concentration of DE and ME (DM basis) in FFRB and DFRB. [ABSTRACT FROM AUTHOR]

The Orgueil meteorite has become one of the most well-studied carbonaceous meteorites, after it fell in France 150 yr ago. Extraterrestrial organic compounds such as amino acids and nucleobases in the parts per billion ranges were identified in Orgueil samples with supporting isotopic analyses. However, speculations of terrestrial contamination such as organic inclusions in the form of microbes and seeds accompanied the analyses of the Orgueil meteorite ever since its fall. By using molecular analysis, we performed DNA extractions and spiking experiments combined with 16S and 18S rRNA gene targeted PCR amplification to quantify the level of terrestrial biocontamination. Our results indicate that terrestrial contamination with DNA was insignificant in the investigated meteorite fraction. We also remeasured and confirmed concentrations of amino acids found in previous studies and conclude that their rather high concentrations and distribution cannot be explained by terrestrial contamination with microorganisms alone. These results represent the first analysis using DNA-directed tools in the analysis of the Orgueil meteorite to determine trace levels of biomarkers. [ABSTRACT FROM AUTHOR]

Organic carbon (OC) accounts for a large fraction of particulate matter. Since many atmospheric organic compounds have different optical properties, it is difficult to determine the optical properties of OC accurately. In particular, hygroscopicity and light absorption of OC are important factors in understanding the aerosol optical properties. In this study, the sensitivity of organic carbon (OC) to aerosol optical properties was tested. Both the refractive index and the hygroscopicity of OC were considered. Based on the filter-based monthly averaged sampling measurement data from an intensive observation site in Seoul, Korea, the contribution of each component on the aerosol optical properties was estimated. The aerosol optical properties were simulated by combining the aerosol dynamic model for polydispersed aerosols with an optical properties model based on Mie code. The optical properties were compared with the AERONET Aerosol Optical Thickness (AOT) measurement data. In order to estimate the contribution of the light absorption and hygroscopicity of organic carbon (OC) on the optical properties of the aerosols, a sensitivity test was conducted with different imaginary refractive indices and OC hygroscopic growth factors. The results show that mass absorption efficiency can be fitted linearly as the imaginary refractive index increases. This means that one can estimate the mass absorption efficiency of OC as a function of the imaginary refractive index. The results also show that mass extinction and absorption efficiency decrease as the hygroscopic factor of OC increases because of the increase in water content. The contribution of OC to the mass extinction efficiency, however, depends on the chemical composition of other aerosol mixtures and hence, more comprehensive studies are required in this regard. [ABSTRACT FROM AUTHOR]

In order to understand the biodegradability of algal-derived organic matter, biodegradation experiments were conducted with C and N-labeled natural phytoplankton and periphytic algal populations in experimental conditions for 60 days. Qualitative changes in the dissolved organic matter were also determined using parallel factor analysis and the stable carbon isotopic composition of the hydrophobic dissolved organic matter through the experimental period. Although algal-derived organic matter is considered to be easily biodegradable, the initial amounts of total organic carbon newly produced by phytoplankton and periphytic algae remained approximately 16 and 44 % after 60 days, respectively, and about 22 and 43 % of newly produced particulate nitrogen remained. Further, the dissolved organic carbon derived from both algal populations increased significantly after 60 days. Although the dissolved organic matter gradually became refractory, the contributions of the algal-derived organic matter to the dissolved organic matter and hydrophobic dissolved organic matter increased. Our laboratory experimental results suggest that algal-derived organic matter produced by phytoplankton and periphytic algae could contribute significantly to the non-biodegradable organic matter through microbial transformations. [ABSTRACT FROM AUTHOR]

Profound understanding of behaviors of organic matter from sources to multistage rivers assists watershed management for improving water quality of river networks in rural areas. Ninety-one water samples were collected from the three orders of receiving rivers in a typical combined polluted subcatchment (diffuse agricultural pollutants and domestic sewage) located in China. Then, the fluorescent dissolved organic matter (FDOM) information for these samples was determined by the excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC). Consequently, two typical humic-like (C1 and C2) and other two protein-like (C3 and C4) components were separated. Their fluorescence peaks were located at λ = 255(360)/455, <250(320)/395, 275/335, and <250/305 nm, which resembled the traditional peaks of A + C, A + M, T, and B, respectively. In addition, C1 and C2 accounted for the dominant contributions to FDOM (>60 %). Principal component analysis (PCA) further demonstrated that, except for the autochthonous produced C4, the allochthonous components (C1 and C2) had the same terrestrial origins, but C3 might possess the separate anthropogenic and biological sources. Moreover, the spatial heterogeneity of contamination levels was noticeable in multistage rivers, and the allochthonous FDOM was gradually homogenized along the migration directions. Interestingly, the average content of the first three PARAFAC components in secondary tributaries and source pollutants had significantly higher levels than that in subsequent receiving rivers, thus suggesting that the supervision and remediation for secondary tributaries would play a prominent role in watershed management works. [ABSTRACT FROM AUTHOR]

To assess whether sea floor sediment reflects the characteristics of the upper water column, organic carbon (OC) and biogenic silica (bSi) were measured in seventeen 5-cm-long sediment cores recovered within a climatic gradient from the northwestern Weddell Sea (WS) to the Drake Passage (DP) across the Bransfield Strait (BS). Climate settings in the study area vary from dry and cold (polar) conditions with seasonal sea ice coverage in the WS to a more humid and warm (oceanic) environment where no seasonal sea ice develops in the DP, with the BS as transitional zone undergoing seasonal sea ice coverage. OC varied between 0.2 and 1.7 % and represented more than 90 % of the total carbon, and bSi varied between 2 and 13 %. The profiles of both variables along the sediment cores suggested that the surface mixed layer is at least 5 cm thick. The inventories of the upper 5 cm of the sediment column were calculated for both variables. Regional averages were significantly lower for OC in DP samples and higher for bSi in the BS. These results suggested relatively high bSi export to the seabed in the BS, higher degradation for OC in the DP and lower bSi export from the euphotic zone in the WS. The observations made evident that the biogenic matter contents in the sediment not necessarily replicate their production characteristics at the upper ocean even across strong climatic gradients. The results may provide a useful baseline for paleo-reconstructions in a rapidly changing environment. [ABSTRACT FROM AUTHOR]

In the current study, we report the preparation of modified biosorbent from Spirulina platensis microalga via the high light application in order to enhance its dye biosorption capacity. The modified biosorbent was characterized with analyses of content of phenolic compounds, FTIR and SEM. The biosorbent was applied to kinetic and equilibrium studies for removal of C.I. Basic Red 46 (C.I. BR 46) from aqueous solution. The kinetic data were best described by the logistic model, while the equilibrium data were best fitted by Langmuir model. The kinetic and isotherm studies indicated that C.I. BR 46 biosorption onto the modified biosorbent occurred in monolayers and the biosorption process was controlled by physical sorption. The level of phenolic compounds in the high light applied biosorbent was defined approximately eightfold higher than in the native biosorbent. Moreover, the high light application provided an increase in the dye biosorption capacity of about 31%, when compared to the raw biosorbent. The maximum biosorption capacity of modified biosorbent was found to be 33.33 mg g-1 for C.I. BR 46 at the worked biosorption conditions. Thus, this work reveals that high light application can potentially be used to increase biosorption capacity of biosorbents. [ABSTRACT FROM AUTHOR]

Kinetic size exclusion chromatography with mass spectrometry detection (KSEC-MS) is a solution-based label-free approach for studying kinetics of reversible binding of a small molecule to a protein. Extraction of kinetic data from KSEC-MS chromatograms is greatly complicated by the lack of separation between the protein and protein-small molecule complex. As a result, a sophisticated time-consuming numerical approach was used for the determination of rate constants in the proof-of-principle works on KSEC-MS. Here, we suggest the first non-numerical (analytical) approach for finding rate constants of protein-small molecule interaction from KSEC-MS data. The approach is based on the slow-equilibration approximation, which is applicable to KSEC-MS chromatograms that reveal two peaks. The analysis of errors shows that the slow-equilibration approximation guarantees that the errors in the rate constants are below 20% if the ratio between the characteristic separation and equilibration times does not exceed 0.1. The latter condition can typically be satisfied for specific interactions such as receptor-ligand or protein-drug. The suggested analytical solution equips analytical scientists with a simple and fast tool for processing KSEC-MS data. Moreover, a similar approach can be potentially developed for kinetic analysis of protein-small molecule binding by other kinetic-separation methods such as nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM). [ABSTRACT FROM AUTHOR]

Dynamic structure of Soman diastereoisomers has been studied with the goal of obtaining accurate information to simulate molecular mechanisms of its action on living systems. The potential energy surface for internal rotation about the single P-O and O-C bonds has been constructed in terms of the Møller-Plesset second-order perturbation theory using 6-311G( d, p) basis set. The relative contributions of different conformers have been estimated by solving the vibrational problem according to the large-amplitude vibration model. The conformational dependences of the J and J coupling constants for the S, S and S, R diastereoisomers of Soman have been calculated at the FPT DFT B3LYP/6-311++G(2 df,2 p) level of theory. The calculated vibrationally averaged coupling constants have been compared with the available experimental data to determine the structure of the most toxic Soman stereoisomer. [ABSTRACT FROM AUTHOR]

Small rivers and streams are ecologically important because they contribute to the export of organic carbon to coastal environments, likely influencing the global carbon cycle. While organic matter (OM) dynamics in large rivers has been studied in quite some detail, less is known about small streams. Sources of OM in streams ultimately determine its availability to the food web and downstream transport. In this study, sediment samples were collected from the King's Creek watershed in Konza Prairie (Kansas, USA) and analyzed using molecular biomarkers and bulk C stable isotopes with the objective to comparatively assess OM inputs between riparian forest vegetation and watershed grassland to small, intermittent streams. We are interested in the potential influence of woody riparian expansion that has been ongoing at the site. Biomarkers typical of the local C grasses (branched n-alkanes, phytadienes) were more abundant in some of the sediments of the upper reaches. The sediments of the lower reaches contained biomarkers of algae (short-chain aliphatic compounds, C highly branched isoprenoid, brassicasterol) and vascular plant-derived material (triterpenols). Degraded OM (triterpene/triterpenol ratio) was found throughout the watershed with no pattern between the upper and lower reaches. Bulk C isotope analysis showed that the upper reaches of the watershed receive significant OM inputs from the C grasses (74-99 %) while the lower reaches are more strongly influenced by riparian trees (26-27 %) and algae (21-22 %). These results suggest that the environmental dynamics of bulk OM and the biomarker composition of small prairie streams are highly complex and likely a function of several factors such as light availability, riparian vegetative composition and density, and varying degrees of OM storage, retention and transport along the river continuum. [ABSTRACT FROM AUTHOR]

One option to sustain full-sun coffee plantation is the use of a 'cut-and-carry' system in which a stand of N-fixing trees is grown outside the coffee field and utilized as a source of mulch to capture the benefits of organic matter, nutrient additions, and continuous soil cover. The objectives of this study were to evaluate the potential of a cut-and-carry system of mulch additions from a multipurpose N-fixing tree for open-grown coffee in Hawaii to support high crop yield as well as improved soil organic matter and nitrogen. A stand of Leucaena variety KX2 trees were pollarded every 6 months, and the pollarded material was chipped and added to open-grown coffee plots. Approximately 65 Mg ha of mulch dry matter was added over a 3-year period, including ~27.5 Mg ha of C and ~530 kg ha of total N. Plots without mulch addition were fertilized with equivalent amounts of inorganic N for comparison. Mulch decomposition averaged 64 % (weight basis) over the first year and followed first-order decay dynamics. Net N mineralization was positive by 3 months after addition. There was significant loss of all major biochemical components during the decomposition process. Mulching increased soil CO efflux by 2.89 Mg ha. Total soil C and N increased by 2.90 and 1.42 Mg ha, respectively. Mulch addition significantly increased all measures of coffee growth and yield over 2 years, except for average bean weight. Where space is available or shade is undesirable, a cut-and-carry mulching system using Leucaena-KX2 can increase soil C and N and achieve coffee yields similar to or greater than other full-sun systems. [ABSTRACT FROM AUTHOR]