Measurement of ethylene and methane production in a temperate forest soil using inhibition of acetylene and carbon monoxide

We studied in the laboratory the effects of acetylene （C2H2） concentrations on the accumulation and consumption of ethylene and methane in a temperate pine forest soil, and in situ ethylene and methane production and flush effects of nitrogen sources on both productions in the pine forest stand （Pinus sylvestris L.）. The addition of C2H2 at concentrations more than 50 Pa C2H2 in the headspace caused a more than 95% reduction in rates of ethylene and methane consumption in forest soil compared to those with no C2H2. Furthermore, addition of acetylene within a range of 50 to 10, 000 Pa C2H2 induced a similar rate of methane accumulation in forest soil. Hence, it can be concluded that presence of more than 50 Pa C2H2 in the headspace is an effective method to measure methane production in forest soil. The addition of C2H2 at concentrations more than 50 Pa C2H2 induced an increasing concentration of ethylene in the headspace （P≤0.05）, indicating the reduction of acetylene to ethylene in forest soil. Using inhibition of 0.5 kPa C2H2 in combination with 5 kPa carbon monoxide that inhibits the reduction of acetylene in a short term, it was observed that there was a larger in situ methane production rate （218±26 μg C m^-2 h^-1（μg C per square meter per hour, the same below）） than in situ ethylene production rate （92±6 μg C m^-2 h^-1） in the pine forest soil. The addition of nitrogen sources such as urea, urea plus a nitrification inhibitor dicyandiamide, and potassium nitrate, could induce a 5-fold greater increase in rates of in situ ethylene and methane production compared to those in the control, particularly in the latter （P≤0.05）. The results can promote in situ measurement of ethylene and methane production in forest soils at different sites.     

Investigation of adsorption of surfactant at the air-water interface with quantum chemistry method

Density functional theory （DFT） of quantum chemistry was used to optimize the configuration of the anionic surfactant complexes CH3（CH2）7OSO3^- （H2O）n （n=0-6） and calculate their molecular frequencies at the B3LYP/6-311＋G^＊ level. The interaction of CH3（CH2）7OSO3^- with 1 to 6 water molecules was investigated at the air-water interface with DFT. The results revealed that the hydration shell was formed in the form of H-bond between the hydrophilic group of CH3（CH2）7OSO3^- and 6 waters. The strength of H-bonds belongs to medium. Binding free energy revealed that the hydration shell was stable. The increase of the number of water molecules will cause increases of the total charge of hydrophilic group and S10-O9-C8 bond angle, but decreases of the alkyl chain length and the bond lengths of S10-O11, S10-O12 as well as S10-O13, respectively.     

Formation, structure and properties of GeCn± and Ge2Cn± binary clusters

The binary cluster ions Ge₂C_n⁺/Ge₂C_n^- and GeC_n⁺ have been produced by laser ablation. The parity effect is present in the negative ions Ge₂C_n^-, though it is not very prominent. While the experiments tell that the parity effect is totally not shown in the positive ions Ge₂C_n⁺. An extensive theoretical investigation on GeCn/GeC_n⁺/GeC_n^-(n=1-10) and Ge₂Cn/Ge₂C_n⁺/Ge₂C_n^-(n=1-9) has been carried out by density functional theory at B3LPY level. The calculation shows that the low-lying states of GeC_n/GeC_n⁺/GeC_n^-(n=1-10) and Ge₂C_n/Ge₂C_n⁺/Ge₂C_n^-(n=1-9) are linear structure with germanium atoms locating at terminals respectively. The electronic distributions, ionization potential (IP_ad), elec-tron affinity (EA) and increasing bonding energy reveal that the parity effect of neutral species is much stronger than that of ions, which is attributed to the valence π-electrons. It is explained that the differences between experiments and cal-culations are due to the kinetic factor in the formation of Ge₂C_n^±.     

Effects of nitrogen sources and glucose on the consumption of ethylene and methane by temperate volcanic forest surface soils

There is limited knowledge with regard to the consumption of ethylene (C2H4) and methane (CH4) in volcanic forest soils containing low microbial carbon-to-organic carbon ratio, and to the responses of both consumptions to nitrogen and carbon additions. Temperate volcanic forest surface soils under three forest stands (e.g. Pinus sylvestris L., Cryptomeria japonica and Quercus serrata) were used to compare CH4 and C2H4 consumption by forest soils, and to study the effects of nitrogen sources and glucose on both consumptions. There was a good parallel between CH4 and C2H4 consumption by for- est soils, but mineralization reduced CH4 consumption rather than C2H4 consumption in forest soils, particularly in a Pinus forest soil. The stimulatory effect of glucose addition on both CH4 and C2H4 consumption by forest soils was increased by increasing the pre-incubation period after glucose addi- tion, and a largest stimulation occurred in the Pinus forest soil. The addition of KNO3-N at the rate of 100 μg·g1 significantly reduced the consumptions of both C2H4 and CH4 by forest soils (P≤0.05). In the presence of urea plus dicyandiamide, the consumption rates of C2H4 and CH4 by forest soils were higher than those in the KNO3-N and urea-N treated soils at the same N rate (P≤0.05), but were similar to those of the control. Hence, under experimental conditions, there was a strong inhibitory effect of NO3 rather than NH4 addition on the CH4 and C2H4 consumption in these forest soils. When amount of the added NO3-N increased up to more than 2―3 times the soil initial NO3-N concentrations, both C2H4 and CH4 consumption rates were reduced to 10%―20% of the rates in soils without nitrate addition. By comparing the three forest stands, it was shown that there was a smallest effective concentration of the added nitrate that could inhibit C2H4 and CH4 consumption in the Pinus forest soil, which indicated that C2H4 and CH4 consumption of the soil was more sensitive to NO3-N addition.     

Temperature effects on ethylene and methane production from temperate forest soils

Change in temperature affects the activity of soil microorganisms.However,there is limited knowledge about temperature effects on ethylene(C2H4) and methane(CH4) production from forest soils.Topsoil samples(0―5 cm) collected from different temperate forest stands(e.g.,Pinus sylvestris L.,Cryptomeria japonica,and Quercus serrata) were used to compare C2H4 and CH4 production from soils at temperature from 5 to 35℃ under oxic and anoxic conditions.The rates of C2H4 and CH4 production from soils under oxic cond...     

Effects of synthetic conditions on the structure and morphology of open-ended vanadium oxide nanotubes and study of their growth mechanism

Vanadium oxide nanotubes (VOx-NTs) have been synthesized by using n-butylamine as structuredirecting template and V2O5 as precursor under hydrothermal conditions. XRD, FTIR, SEM, TEM, BET and TG-DTA characterizations have been performed to both optimize the synthetic conditions and understand the growth mechanism of VOx-NTs. The results showed that open-ended VOx-NTs were obtained under the optimized conditions (hydrothermal temperature: 150―160°C, hydrothermal time: 5―7 d, the molar ratio of V2O5 to n-butylamine is 1:1) with diameters ranging from about 30 to 100 nm and several micrometers in length. The BET surface area and the desorption cumulative pore volume of pores of the as-synthesized sample were about 27.4609 m2/g and 0.191087 cm3/g, respectively. The result presents that the synthesis of VOx-NTs is controlled by the "rolling" mechanism and temperature is primary driving force for rolling.     

Styrene polymerization catalyzed by nickel complexes bearing hydroxyindanone-iminate ligands

Activated by methylaluminoxane, mononuclear bis（hydroxyindanone-iminate）nickel complexes Ni[ArN=CC2H3（CH3）C6H2（R）O]2 （Ar = 2,6-i-Pr2C6H3, R=Me（1）, R=CI（2）, and R=H（3）） showed good activity for the styrene polymerization. The effect of many reaction parameters including the AI/Ni ratio, temperature, and reaction time on catalytic activities of catalytic systems and the molecular weights of the obrained polystyrene was ascertained. The highest activity of 1.34×10^5g（PS）·mol^-1（Ni）·h^-1 was obtained under the optimum reaction condition. The ^13C NMR spectra of the polymers revealed that the polymer was isotactic-rich atactic polystyrene. And the coordination mechanism was confirmed by the analyses of the polymer chain end-groups.     

Effects of acetylene at low concentrations on nitrification, mineralization and microbial biomass nitrogen concentrations in forest soils

Temperate forest surface soils at the varying distances from main trunks (e.g., Pinus koraiensis and Quercus mongolica) were used to study the effects of acetylene (C₂H₂) at low concentrations on nitrification, mineralization and microbial biomass N concentrations of the soils, and to assess the contribution of heterotrophic nitrification to nitrous oxide (N₂O) emissions from soils. The use of acetylene at partial pressures within a range from 10 to 100 Pa C₂H₂ in headspace gas gave a significant decrease in N₂O emission at soil moisture of c. 45% water-filled porosity space, and the decrease was almost the same in each soil after exposure of C₂H₂ at low concentrations. Heterotrophic nitrification could account for 21%―48% of total N₂O emission from each soil; the contribution would increase with increasing distances from the Pinus koraiensis trunks rather than from the Quercus mongolica trunks. Under the experimental conditions, the use of C₂H₂ at low concentrations showed no significant influence on soil microbial biomass N, net N mineralization and microbial respiration. However, 100 Pa C₂H₂ in headspace gas could reduce carbon dioxide (CO₂) emissions from soils. According to the rapid consumption of 10 Pa C₂H₂ by forest soils and convenience for laboratory incubations, 50 Pa C₂H₂ in headspace gas can be used to study the origin of N₂O emissions from forest soils under aerobic conditions and the key associated driving mechanisms. The N₂O and CO₂ emissions from the soils at the same distances from the Quercus mongolica trunks were larger than those from the Pinus koraiensis trunks, and both emissions decreased as the distances from trunks increased. The stepwise regression analysis showed that 95% of the variability in soil CO₂ emissions could be accounted for by the concentrations of soil total C and water soluble organic C and soil pH, and that 72% of the variability in soil N₂O emissions could be accounted for by the concentrations of soil total N, exchangeable NH⁺₄-N and microbial biomass N and 25% of the variability in heterotrophic nitrification by the soil microbial biomass N concentration. The emissions of N₂O and CO₂ from forest soils after exposure of C₂H₂ at low concentrations were positively related to the net nitrification of the soils.     

Theoretical study of partial oxidation of ethylene by vanadium trioxide cluster cation

Density functional theory （DFT） study of reaction between vanadium trioxide cluster cation （VO3^＋） and ethylene （C2H4） to yield VO2^＋ ＋ CH3CHO （acetaldehyde） and VO2CH2^＋ ＋ HCHO （formaldehyde） is carried out. Structures of all reactants, products, intermediates, and transition state in the reaction have been optimized and characterized. The results show unexpected barriers in the reaction due to the existence of a η^2-O2 moiety in the ground state structure of VO3^＋. The initial reaction steps combining ethylene adsorption, C=C activation and O-O cleavage are proposed as rate limiting processes. Comparison of reactions of VO3^＋ ＋ C2H4 with VO3 ＋ C2H4 and VO2^＋ ＋ C2H4 in the previous studies is made in detail. The results of this work may shed light on the understanding of C=C bond cleavage in related heterogeneous catalysis.     

The uptake of ethyl iodide on black carbon surface

The importance of the iodine chemistry in the atmosphere has been demonstrated by recent obserations. The uptake of ethyl iodine on black carbon surface was inestigated at 298 K for the first time. Degussa FW2 （an amorphous black carbon comprising medium oxides） was used as black carbon sample. Black carbon surface was found to be deactiated in reaction with C2H51, and the uptake coefficient （r） was dependent on the time of exposure. The alue of （2.3±0.9）×10^-2 was determined for the initial uptake coefficient （No）. The result suggests that the heterogeneous loss of C2H51 on carbonaceous aerosols may be important under the atmospheric conditions.     

Modification of TiO2 nanotubes arrays by CdS and their photoelectrocatalytic hydrogen generation properties

In order to realize hydrogen generation under visible light, novel CdS/TiO2 nanotubes arrays are developed by electrochemical anodizaUon of Ti in 0.15 mol/L NHTF ＋ 0.08 mol/L H2C2O4 electrolyte. The diameter of the nanotube is 80-100 nm and the length is approximately 550 nm. The CdS nano-particles are deposited on the TiO2 nanotubes arrays by chemical bath deposition （CBD） in the ammonia-thiourea system. A 300 W Xe lamp is used as the light source, CdS/TiO2 nanotube arrays are used as the photoanode with the application of 1.0 V bath voltage, and 0.1 mol/L Na2S ＋ 0.04 mol/L Na2SO3 solution is used as the electrolyte, then the rate of photoelectrocatalytic hydrogen generation is 245.4 μL/（h·cm^2）. This opens new perspectives for photoelectrocatalytic hydrogen generation by using CdS/TiO2 nanotubes arrays.     

Rate constants for the reaction of ozone with <Emphasis Type="Italic">n</Emphasis>-butyl, <Emphasis Type="Italic">s</Emphasis>-butyl and <Emphasis Type="Italic">t</Emphasis>-butyl methyl sulfides

The rate constants for the ozone reactions with n-butyl methyl sulfide （n-BMS, CHaCH2CH2CH2SCH3）, sec-butyl methyl sulfide （s-BMS, CH3CH2（CH3）CHSCHa） and tert-butyl methyl sulfide （t-BMS, （CH3）3CSCH3） were measured using our smog chamber under supposedly pseudo-first-order conditions at 30002 K and 760 Torr. The experimental determined rate constants for n-butyl, s-butyl and t-butyl methyl sulfide are （1.23 ± 0.06）×10-19, （5.08 ± 0.19）×10-20 and （2.26 ± 0.14）×10-20 cm3 molecule-1· s-1, respectively. The reactivity-structure relationship of the reactions was discussed and used to illustrate the mechanism of the ozone reaction with thioethers. The results enrich the kinetics data of atmospheric chemistry.     

Holocene climatic and environmental changes recorded in Baahar Nuur Lake core in the Ordos Plateau, Inner Mongolia of China

A 5.3 m lake core was drilled in Baahar Nuur Lake in the Ordos Plateau, and measurements of meangrain size, organic δ 13C (δ 13Corg), organic carbon content (TOC), C/N, carbonate content, carbonate δ 13C(δ 13Ccar) and δ 18O (δ 18Ocar) were conducted for retrieving the Holocene chronosequence of climaticchanges based on 15 AMS 14C dates. The record documented four major stages of climate change inthe Ordos Plateau: (IV) a cold and dry condition before ～7.65 14C ka BP; (III) a warm and humid stagebetween ～7.65 and ～5.40 ka BP; (II) a generally drier and cooler climate since ～5.40 ka BP with twohumid events occurring from ～4.70 to ～4.60 ka BP and from ～4.20 to ～3.70 ka BP, and (I) a dry climatecharacterized by complete desiccation of the lake after 3.70 ka BP. Stage III can be further divided intothree sub-stages: (IIIa) a warm and humid episode from ～7.65 to ～6.70 ka BP, (IIIb) a warm and relativelydry episode from ～6.70 to ～6.20 ka BP, and (IIIc) the magthermal and maghumid episode of the Holo-cene from ～6.20 to ～5.40 ka BP.     

Low temperature thermodynamic study of the stable and metastable phases of vanadium

The low temperature thermodynamics of the stable phase of vanadium has been assessed by the polynomial and Debye models from the experimental data available in literature. By means of the con-strained nonlinear least squares curve fitting arithmetic,two sets of parameter values have been de-termined. Expressions of the thermodynamic functions Cp(T) and G(T)-H(298.15 K) at 0―298.15 K are presented. The low temperature thermodynamics of the metastable phase of vanadium can only be extrapolated by the Debye model. The expression of the thermodynamic function Cp(T) at 0―298.15 K is presented.     

THz spectra of five borates crystals

Terahertz spectral responses have been studied for five borate crystals Nas[B2P3O13] （NBP）, Zn3BPO （ZBP）, SrB407 （SBO）, Na3LagO3（BO 3）8 （NLBO） and PbB407 （PBO）. It is found that the samples had good transmission in 0.25--1.5 THz region. Both SBO and NLBO have an absorption coefficient less than 10 cm^-1. Among them, SBO has not only the smallest absorption coefficient but also a very flat dispersion in the frequency region under investigation. Distinct resonance absorption peaks are observed for ZBP at v1 = 1.4 THz, v2 = 2.0 THz and SBO at v = 2.4 THz. In the spectrum of PBO, two abnormal dispersions appear in the frequency regions 1.44--1.74 and 2.2--2.5 THz. The absorption coefficients and refraction indices of the five crystals are extracted from the THz time-domain （THz-TDS） spectra in 0.25--2.5 THz region. The properties and origins of the spectral responses are addressed.     

Inorganic-organic hybrids constructed of bis（undecatungstogerma- nate）lanthanates polyoxoanions and oxalate-bridged dinuclear copper complexes and their magnetic properties

A series of inorganic-organic hybrids K₂Na _m H_9−m [{Ln(GeW₁₁O₃₉)₂}{Cu₂(bpy)₂(μ-ox)}]·nH₂O (bpy = 2,2-bipyridine and ox = oxalate; Ln = La, Nd, Sm, Eu, Gd; n = 19, 17, 22, 20, 19; m = 4, 4, 4, 9, 2) were isolated after reacting in a potassium acetate buffer. X-ray structural analyses show that compounds 1–5 are isomorphic and consist of [Ln(GeW₁₁O₃₉)₂]¹³⁻ polyoxoanion building blocks and oxalate-bridged dinuclear copper metalorganic complex with a 1D chain structure. The 1D chain further connects into the 3D framework by π-π interactions with neighboring bpy groups. The magnetic susceptibility data indicate that antiferromagnetic coupling between the neighboring Cu²⁺ ions in the structure and the rare earth ions affects magnetic property of the structure.     

Analysis of active sites for N2 and H^＋ reduction on FeMo-cofactor of nitrogenase

Dinitrogen (N2) and proton (H ),which act as physiological substrates of nitrogenase,are reduced on FeMo-co of the MoFe protein. However,researchers have different opinions about their exact reduction sites. Nitrogenases were purified from the wild type (WT) and five mutants of Azotobacter vinelandii (Av),including Qα191K,Hα195Q,nifV-,Qα191K/nifV- and Hα195Q/nifV-; and the activities of these en-zymes for N2 and H reduction were analyzed. Our results suggest that the Fe2 and Fe6,atoms closed to the central sulfur atom (S2B) within FeMo-co,are sites for N2 binding and reduction and the Mo atom of FeMo-co is the site for H reduction. Combining these data with further bioinformatical analysis,we propose that two parallel electron channels may exist between the 8Fe7S cluster and FeMo-co.     

Direct electrochemistry and electrocatalysis of horseradish peroxidase in MnO2 nanosheet film

A novel material MnO2 nanosheet has been used as the support matrix for the immobilization of horseradish peroxidase （HRP）. HRP entrapped in MnO2 nanosheet film exhibits facile direct electron transfer with the electron transfer rate constant of 6.86 s^-1. The HRP/MnO2 nanosheet film gives a reversible redox couple with the apparent formal peak potential （E^0＇） of -0.315 V （vs. Ag/AgCl） in pH 6.5 phosphate buffer solution （PBS）. The formal potential E^0＇ of HRP shifts linearly with pH with a slope of -53.75 mV.pH^-1, denoting that an electron transfer accompanies single-proton transportation. The immobilized HRP shows an electrocatslytic activity to the reduction of H2O2. The response time of the biosensor for H2O2 is less than 3 s, and the detection limit is 0.21 μmol · L^-1 based on signal/noise = 3.     

Site-directed mutagenesis reveals new and essential elements for iron-coordination of the sulfur oxygenase reductase from the acidothermophilic Acidianus tengchongensis

Previous study on refolding of sulfur oxygenase reductase (SOR) inclusion bodies from recombinant Escherichia coli showed that iron was critical to the activity of the SOR from Acidianus ambivalens. In this study, enzymatic assays showed that 2,2′-Dipyridyl, Tiron and 8-hydroxyquinoline, which are specific for chelating ferrous or ferric ions, strongly inhibited the activity of SOR from A. tengchongensis, suggesting that iron atom is essential for SOR activity. Alignment of several functionally identified SORs and SOR-like sequences from genome database revealed a conserved, putative iron binding motif, H⁸⁶-X₃-H⁹⁰-X _n -E¹¹⁴-X _n -E¹²⁹ (numbering according to the Acidianus tengchongensis SOR sequence). Three mutants of SOR were generated by site-directed mutagenesis of H₈₆, H₉₀ and E₁₂₉ into phenylalanine or alanine residue in this study. Circular dichroism spectrum determination indicated that there was no change of the secondary structures of mutant SORs, H⁸⁶F, H⁹⁰F and E¹²⁹A, but all mutants were completely inactive. Through determination of iron contents we found that SOR mutants of H⁸⁶F, H⁹⁰F and E¹²⁹A completely or partially lost iron, while mutants of C³¹S, C¹⁰¹S, and C¹⁰⁴S (generated in a previous study) did not. This result indicated that H⁸⁶, H⁹⁰ and E¹²⁹ but not C³¹, C¹⁰¹, and C¹⁰⁴ were involved in binding to iron atom. Based on this and previous studies, it is proposed that the conserved motifs, C³¹-X _n -C¹⁰¹-X₂-C¹⁰⁴ and H⁸⁶-X₃-H⁹⁰-X₂₃-E¹¹⁴-X₁₄-(E/D)¹²⁹, are respectively for sulfur and molecular oxygen binding and activation. These two conserved motifs are essential elements for the SOR activity. Supported by National Natural Science Foundation of China (Grant Nos. 30670018, 30621005) and State Key Basic Research and Development Program of China (Grant No. 2004CB719602)     

Comparison of the carbon isotope composition of total organic carbon and long-chain <Emphasis Type="Italic">n</Emphasis>-alkanes from surface soils in eastern China and their significance

Surface soil samples collected over a high spatial resolution in eastern China were analyzed for carbon isotope composition （δ^13C） of total organic carbon （TOC） and higher plant-derived long-chain n-alkanes, with the latter reported as weighted mean values. The two sets of δ^13C values are significantly correlated and show similar trends in spatial variation. The spatial distribution of δ^13C shows less negative values in the mid-latitudes between 31°N and 40°N and more negative ones at higher and lower latitudes. This is consistent with previously reported carbon isotope data from surface soil phytoliths in the same region and suggests that the mid-latitude area provides relatively favorable growing condi- tions for C4 plants. Furthermore, δ^13C values of both TOC and long-chain n-alkanes from 12 surface soil samples collected from a small grassland in north China displayed similar carbon isotope values and the difference between paired δ^13C of a soil samples remains relatively constant. Our data demonstrate that in eastern China, soil δ^13C composition of both TOC and long-chain n-alkanes is effective indicators of C3/C4 ratios of the prevailing vegetation. This work suggests that -22‰ and -32‰ are good es- timated end members for the weighted mean δ^13C values of long-chain n-alkanes （C27, C29 and C31 n-alkanes） from soils under dominant C4 or C3 vegetation, allowing us to reconstruct paleovegetation trends.