Coral reef ecosystems in the South China Sea as a source of atmospheric CO<Subscript>2</Subscript> in summer

Field measurements of air-sea CO2 exchange in three coral reef areas of the South China Sea (i.e. the Yongshu Reef atoll of the Nansha Islands, southern South China Sea (SCS); Yongxing Island of Xisha Islands, north-central SCS; and Luhuitou Fringing Reef in Sanya of Hainan Island, northern SCS) during the summers of 2008 and 2009 revealed that both air and surface seawater partial pressures of CO2 (pCO2) showed regular diurnal cycles. Minimum values occurred in the evening and maximum values in the morning. Air pCO2 in each of the three study areas showed small diurnal variations, while large diurnal variations were ob-served in seawater pCO2. The diurnal variation amplitude of seawater pCO2 was ~70 μmol mol–1 at the Yongshu Reef lagoon, 420–619 μmol mol–1 on the Yongxing Island reef flat, and 264–579 μmol mol–1 on the reef flat of the Luhuitou Fringing Reef, and 324–492 μmol mol–1 in an adjacent area just outside of this fringing reef. With respect to spatial relations, there were large differences in air-sea CO2 flux across the South China Sea (e.g. ~0.4 mmol CO2 m–2 d–1 at Yongshu Reef, ~4.7 mmol CO2 m–2 d–1 at Yongxing Island, and ~9.8 mmol CO2 m–2 d–1 at Luhuitou Fringing Reef). However, these positive values suggest that coral reef ecosystems of the SCS may be a net source of CO2 to the atmosphere. Additional analyses indicated that diurnal variations of surface seawater pCO2 in the shallow water reef flat are controlled mainly by biological metabolic processes, while those of deeper water lagoons and outer reef areas are regulated by both biological metabolism and hydrodynamic factors. Unlike the open ocean, inorganic metabolism plays a significant role in influencing seawater pCO2 variations in coral reef ecosystems.     

Comparative study of the net exchange of CO<Subscript>2</Subscript> in 3 types of vegetation ecosystems on the Qinghai-Tibetan Plateau

Using the eddy covariance method, from 1 July 2003 to 30 June 2004, we conducted the observation and analysis of ecosystem CO2 flux in 3 types of alpine meadow vegetation （Kobresia humilis, Potentilla fruticosa shrub and Kobresia tibetica swamp meadows） on the Qinghai-Tibetan Plateau. The results show that the Kobresia humilis meadow, the shrub meadow and the swamp meadow＇s highest CO2 uptake rates are 16.78, 10.42 and 16.57 μmol·m^-2·-s^-1 respectively, while their highest CO2 release rates are 8.22, 7.73 and 18.67μmol·m^-2·-s^-1 respectively. The Kobresia humilis meadow and shrub meadow＇s annual atmospheric uptakes are 282 g CO2/m^2 and 53 g CO2/m^2, respectively, while swamp meadow＇s annual atmospheric release is 478 g CO2/m^2. This proves that the Kobresia humilis meadow and the shrub meadow on the Qinghai-Tibetan Plateau have relatively low potential for CO2 uptake and release compared to C4 grasslands, a number of lowland grasslands, and forests. Moreover, swamp meadow has relatively high release potential. This, in turn, reveals clear differences in carbon source/sink between different types of vegetation in the Qinghai-Tibetan Plateau alpine meadow ecosystem. These differences are mainly brought by differences in the vegetations＇ photosynthetic capacity and soil respiration.     

Electrochemical properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>1.3</Subscript>Ti<Subscript>0.2</Subscript>O<Subscript>4</Subscript>/Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> cells

Spinel compounds LiNi_0.5Mn_1.3Ti_0.2O₄ (LNMTO) and Li₄Ti₅O₁₂ (LTO) were synthesized by different methods. The particle sizes of LNMTO and LTO are 0.5–2 and 0.5–0.8 μm, respectively. The LNMTO/LTO cell exhibits better electrochemical properties at both a low current rate of 0.2C and a high current rate of 1C. When the specific capacity was determined based on the mass of the LNMTO cathode, the LNMTO/LTO cell delivered 137 mA·h·g⁻¹ at 0.2C and 118.2 mA·h·g⁻¹ at 1C, and the corresponding capacity retentions after 30 cycles are 88.5% and 92.4%, respectively.     

Investigation of the cross-reaction mechanism of C<Subscript>6</Subscript>H<Subscript>5</Subscript>F-HNO<Subscript>2</Subscript> aqueous solution irradiated at 355 nm by transient absorbance spectrum technique

The transient absorption spectrum technique was employed to investigate the cross-reaction mechanism of C6H5F-HNO2 aqueous solution irradiated at 355 nm. The characteristic and the kinetic parameters of transient species were also detected. Hydroxyl radical derived from the photolysis of HNO2 was added to monofluorobenzene with a second-order rate constant of （5.83±0.17）×10^9 L·mol^-1·s^-1 to form an adduct, C6H5F…OH, which was able to react with HNO2 as the main reaction pathway with a rate constant of （8.3±0.1）×10^7 L·mol^-1·s^-1. The C6F6…OH adduct can also be decayed by elimination of H2O to yield monofluorophenyl radical C6H4F-. By GC-MS technique, the final products were identified to be monofluorophenol, nitro-monofluorobenzene, nitro-monofluorophenol and para-fluorobiphenyl.     

The giant magnetocaloric effect in Gd<Subscript>5</Subscript>Si<Subscript>2</Subscript>Ge<Subscript>2</Subscript> with low purity gadolinium

The giant magnetocaloric effect Gd5Si2Ge2 alloy was prepared with 99wt% low purity commercial Gd. Powder XRD and magnetic measurements showed that the Gd5Si2Ge2 alloy annealed at 1200℃ for 1h had a significant magnetic- crystallographic first order phase transition at about 270 K. The maximal magnetic entropy change is 17.55 J· kg^-1· K^-1 under a magnetic field change of 0-5 T. The distinct increase of magnetic entropy change belongs to the first-order phase transition from the orthorhombic Gd5Si4-type to the monoclinic Gd5Si2Ge2-type after high temperature heat-treatment.     

Synthesis, Characterization and Calorimetry of Ni（C4H8N2O3）2Cl2

A coordination complex was synthesized from NiCl2 and dipeptide glycylglycine（GG）. It was characterized by element analysis, NMR and TG methods, and then was determined to be Ni（C4HsN2O3）2Cl2. Using an isoperibolic reaction calorimeter, the standard molar enthalpy of formation of Ni（GG）2Cl2（solid） has been determined to be -（1 674.66±2.02） kJ · mol^-1 at 298.15 K.     

Kinetic studies of the decomposition reaction of adducts of dinuclear Fe(Ⅱ)/O2

Kinetic studies of the decomposition reaction of dinuclear Fe(Ⅱ) adducts [Fe₂(N-Et-HPTB){O₂P(OPh)₂}](Cl- O₄)₂ (1) and [Fe₂(N-Et-HPTB) {O₂P(Ph)₂}] (ClO₄)₂ (2) with O₂ have been carried out at low temperature using UV-vis spectra. The decomposition reaction of Fe(Ⅱ)/O₂ adducts was first-order in the experimental conditions, and the activation parameters were obtained. ?H^¹ = 85.62 kJ·mol^-1, ?S¹ = 19.43 J·mol^-1·K^-1 for compound (1) and ?H^¹ = 97.97 kJ·mol^-1, ?S^¹ = 55.68 J·mol^-1·K^-1 for compound (2). These results are similar to those of dioxygen adducts of other metals complexes and natural enzymes such as methane mono- oxygenase (MMOH).     

Trend, seasonal and diurnal variations of atmospheric CO2 in Beijing

The concentration of atmospheric CO₂ in Beijing increased rapidly at a mean growth rate of 3.7% · a⁻¹ from 1993 to 1995. After displaying a peak of (409.7±25.9) μmol · mol⁻¹ in 1995, it decreased slowly. Both the almost stable anthropogenic CO₂ source and increasing biotic CO₂ sink contribute to the drop of CO₂ concentration from 1995 to 2000. The seasonal variation of CO₂ concentration exhibits a clear cycle with a maximum in winter, averaging (426.8±20.6) μmol · mol⁻¹, and a minimum in summer, averaging (369.1±6.1) μmol·mol⁻¹. The seasonal variation of CO₂ concentration is mainly controlled by phenology. The mean diurnal variation of atmospheric CO₂ concentration for a year in Beijing is highly clear: daily maximum CO₂ concentration usually occurs at night, but daily minimum CO₂ concentration does in the daytime, with a mean diurnal difference more than 34.7 μmol·mol⁻¹. It has been revealed that the interannual variations of atmospheric CO₂ concentration in winter and autumn regulated the interannual trend of atmospheric CO₂, whereas the interannual variation of CO₂ concentration in summer affected the general tendency of atmospheric CO₂ in a less degree.     

Electrocatalytic oxidation of H<Subscript>2</Subscript>O<Subscript>2</Subscript> at a carbon paste electrode modified with a nickel (II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(Diethylcarbamoylmethoxy) calix[4] arene complex and its application

Electrochemical behavior of a carbon paste electrode (CPE) modified with nickel(II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(diethylcarbamoylmethoxy) calix[4]arene (Ni (II)-L) complex and its electrocatalytic activity towards the oxidation of hydrogen peroxide were investigated by cyclic voltammetric technique in a 5.0×10⁻² mol/L NaClO₄+1.0×10⁻³ mol/L NaOH solution. It was found that Ni(II)-L acts as an effective catalyst for the oxidation of hydrogen peroxide. The modified electrode exhibited a linear response over a hydrogen peroxide concentrations in the range of 2.0×10⁻⁵−1.0×10⁻⁴ mol/L with a detection limit as low as 1.0×10⁻⁶ mol/L. The relative standard deviation was 3.5% for 5 successive determinations of H₂O₂ at 1.0×10⁻⁵ mol/L. The modified electrode was used successfully in rainwater analysis. Foundation item: Supported by the Natural Science Foundation of Hubei Province (98J040). Biography: Li Chun ya(1972-), Ph. D. candidate, research direction: electroanalysis and electrosynthesis.     

Static opaque chamber-based technique for determination of net exchange of CO<Subscript>2</Subscript> between terrestrial ecosystem and atmosphere

Terrestrial carbon cycling is one of the hotspots in global change issues. In this paper, we presented the rationale for determination of net exchange of CO₂ between terrestrial and the atmosphere (NEE) and the methods for measuring several relevant components. Three key processes for determination of NEE were addressed, including the separation of shoot autotrophic respiration from total CO₂ emissions of the ecosystem, the partition of root respiration from soil CO₂ efflux, and the quantification of rhizodeposition C from NPP. With an understanding of the processes involved in the CO₂ exchange between terrestrial and the atmosphere, we estimated NEE of rice ecosystem in Nanjing based on field measurements of CO₂ emissions and several relevant biotic components as well as abiotic factors. The field measurements of CO₂ emissions were made over the rice-growing seasons in 2001 and 2002 with the static opaque chamber method. Calculations indicated that the seasonal pattern of NEE is comparable for two seasons. Either net carbon emission or fractional carbon fixation occurred during 3 weeks after rice transplanting and thereafter net carbon fixation appeared with an increasing trend as rice growing. Higher net carbon fixation occurred in the rice developmental period from elongating to heading. A decline trend in the fixation was documented after rice heading. The mean daily NEE was -6.06 gC·m⁻² in 2001 season and -7.95 gC·m⁻² in 2002 season, respectively. These values were comparable to the results obtained by Campbell et al. who made field measurements with the Bowen ratio-energy balance technique in irrigated rice, Texas USA. Moreover, the mean daily NEE in this study was also comparable to the values obtained from a Japanese rice paddy with the eddy covariance method under the similar water regime, either drainage course or waterlogged. It is concluded that NEE determined by the static opaque chamber method is comparable and in agreement with those measured by Bowen ratioenergy balance and eddy covariance methods.     

Ionization and dissociation of CH<Subscript>2</Subscript>I<Subscript>2</Subscript> and CH<Subscript>2</Subscript>ICl in femtosecond intense field

With the development of ultrafast laser technique,the femtosecond laser electric field is comparable to themolecular field experienced by valence electrons. In thiscase, the classical quantum mechanical theory, based onperturbation theory, becomes inapplicable. Theoreticalunderstanding of the interaction of molecules with intenselaser radiation is quite difficult. The Coulomb explosionhas been extensively studied[1—10] and explained by somesemiclassical models, such as the above threshold ion…     

Changes of photosynthetic capacity of some plant species under very high CO2 concentrations in Biosphere 2

Conclusions The initial slope of A/ light curve became steep under high CO₂ (700 μmol · mol^-1) compared with that under low CO₂ (350 μmol · mol^-1) for the C₃ species growing in very high CO₂(>2 200 μmol · mol^-1) for a long period. The light compensation points remained unchanged, but the light saturation points were found increased. The ϕ_m,_app and A_max of the C₃ species increased respectively by 79 % and 80 %, while those of C₄ species decreased by 10% and 14%, respectively. The shape of A/light curve of C₄ species did not change. Such results indicated that C₃ species increased the capacity of photosynthesis, while C₄ did not change, otherwise it decreased a little. This work only compared the changes of capacity in photosynthesis of some species under different CO₂ levels in Biosphere 2. We need further investigation on the effects of high CO₂ on the same species outside Biosphere 2, in order to fully undertand the effects and mechanism of response of plants to the elevated CO₂.     

Preconcentration and Separation of Trace Copper in Water Samples with Nanometer-Size TiO2 Colloid and Determination by FAAS

A new absorbent of nanometer-size TiO2 colloid for Cu(Ⅱ) was studied in this work. The adsorption rate could reach above 99% when the pH values were at the range of 5-6. The adsorption balance time, adsorption capacities, and the eluent were investigated. A novel method of trace Cu(Ⅱ) preconcentration and separation with nanometer-size titanium dioxide colloid and determination by flame atomic absorption spectrometry (FAAS) was advanced. The detection limit (3σ) of the method was 1.15 μg· L~(-1) , and the relative standard deviation (R.S.D) was 1.53% (n=6). Environmental sample experiments were also conducted to test the feasibility of the method, and it came out that the recovery rates were between 95.9% and 97.8%.     

Effect of CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>O on gasification dissolution and deep reaction of coke

To more comprehensively analyze the effect of CO₂ and H₂O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO₂ and H₂O using high temperature gas-solid reaction apparatus over the range of 950-1250℃ were studied, and the thermodynamic and kinetic analyses were also performed. The results show that the average reaction rate of coke with H₂O is about 1.3-6.5 times that with CO₂ in the experimental temperature range. At the same temperature, the endothermic effect of coke with H₂O is less than that with CO₂. As the pressure increases, the gasification dissolution reaction of coke shifts to the high-temperature zone. The use of hydrogen-rich fuels is conducive to decreasing the energy consumed inside the blast furnace, and a corresponding high-pressure operation will help to suppress the gasification dissolution reaction of coke and reduce its deterioration. The interfacial chemical reaction is the main rate-limiting step over the experimental temperature range. The activation energies of the reaction of coke with CO₂ and H₂O are 169.23 kJ·mol-1 and 87.13 kJ·mol-1, respectively. Additionally, water vapor is more likely to diffuse into the coke interior at a lower temperature and thus aggravates the deterioration of coke in the middle upper part of blast furnace.     

Doping effect on thermoelectric properties of nonstoichiometric AgSbTe<Subscript>2</Subscript> compounds

Nonstoichiometric ternary thermoelectric materials Ag_0.84Sb_1.15M_0.01Te_2.16 (M=Ce, Yb, Cu) were prepared by a direct melt-quench and hot press process. The carrier concentration of all the samples increased after doping. Thermoelectric properties, namely electrical conductivity, Seebeck coefficient, and thermal conductivity, were measured from 300 to 673 K. The phase transition occurring at about 418 K representing the phase transition from β-Ag₂Te to α-Ag₂Te influenced the electrical transport properties. The electrical conductivities of Ce and Yb doped samples increased after doping from 1.9×10⁴ to 2.5×10⁴ and 2.3×10⁴ S·m⁻¹, respectively, at 673 K. Also, at room temperature, the Seebeck coefficient of the Ce doped sample relatively increased corresponding to the high carrier concentration due to the changes in the band structure. However, all the thermal conductivities increased after doping at low temperature. Because of the higher thermal conductivity, the dimensionless figure of merit ZT of these doped samples has not been improved.     

Comparative analysis of the dissolution kinetics of galena in binary solutions of HCl/FeCl<Subscript>3</Subscript> and HCl/H<Subscript>2</Subscript>O<Subscript>2</Subscript>

A comparative study of the dissolution kinetics of galena ore in binary solutions of FeCl₃/HCl and H₂O₂/HCl has been undertaken. The dissolution kinetics of the galena was found to depend on leachant concentration, reaction temperature, stirring speed, solid-to-liquid ratio, and particle diameter. The dissolution rate of galena ore increases with the increase of leachant concentration, reaction temperature, and stirring speed, while it decreases with the increase of solid-to-liquid ratio and particle diameter. The activation energy (E _a) of 26.5 kJ/mol was obtained for galena ore dissolution in 0.3 M FeCl₃/8.06 M HCl, and it suggests the surface diffusion model for the leaching reaction, while the E _a value of 40.6 kJ/mol was obtained for its dissolution in 8.06 M H₂O₂/8.06 M HCl, which suggests the surface chemical reaction model for the leaching reaction. Furthermore, the linear relationship between rate constants and the reciprocal of particle radius supports the fact that dissolution is controlled by the surface reaction in the two cases. Finally, the rate of reaction based on the reaction-controlled process has been described by a semiempirical mathematical model. The Arrhenius and reaction constants of 11.023 s⁻¹, 1.25×10⁴ and 3.65×10² s⁻¹, 8.02×10⁶ were calculated for the 0.3 M FeCl₃/8.06 M HCl and 8.06 M H₂O₂/8.06 M HCl binary solutions, respectively.     

Compression behavior and equation of state of Ni77P23 amorphous alloy

The compression behavior of Ni77P23 amorphous alloy is investigated at room temperature in a diamond-anvil cell instrument using insitu high pressure energy dispersive X-ray diffraction with a syn- chrotron radiation source. The equation of state is determined by fitting the experimental data accord- ing to Birch-Murnaghan equation: -ΔV/V0=0.08606P-3.2×10-4P2 5.7×10-6P3. It is found that the structure of Ni77P23 amorphous alloy is stable under pressures up to 30.5 GPa.     

Catalysis of organic pollutant photodegradation by metal phthalocyanines immobilized on TiO<Subscript>2</Subscript>@SiO<Subscript>2</Subscript>

A TiO2@SiO2 hybrid support was prepared by the sol-precipitation method using n-octylamine as a template.The photocatalyst manganese phthalocyanine tetrasulfonic acid (MnPcS) was immobilized on the support to form MnPcS-TiO2@SiO2.X-ray diffraction (XRD) and UV-Visible diffuse reflectance spectra (UV-Vis DRS) were employed to characterize the catalyst.The photocatalytic degradation of rhodamine B (RhB) and the catalytic oxidation of o-phenylenediamine (OPDA) under visible light irradiation were used as probe reactions.The mineralization efficiency and the degradation mechanism were evaluated using chemical oxygen demand (COD Cr) assays and electron spin resonance (ESR),respectively.RhB was efficiently degraded by immobilized MnPcS-TiO2@SiO2 under visible light irradiation.Complete decolorization of RhB occurred after 240 min of irradiation and 64.02% COD Cr removal occurred after 24 h of irradiation.ESR results indicated that the oxidation process was dominated by the hydroxyl radical (·OH) and superoxide radical (O-·2) generated in the system.     

Influence of post-annealing on the properties of Ta-doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> transparent conductive films

Ta-doped In₂O₃ transparent conductive oxide films were deposited on glass substrates using radio-frequency (RF) sputtering at 300°C. The influence of post-annealing on the structural, morphologic, electrical and optical properties of the films was investigated using X-ray diffraction, field emission scanning electron microscopy, Hall measurements and optical transmission spectroscopy. The obtained films were polycrystalline with a cubic structure and were preferentially oriented in the (222) crystallographic direction. The lowest resistivity, 5.1×10⁻⁴ Ω cm, was obtained in the film annealed at 500°C, which is half of that of the un-annealed film (9.9×10⁻⁴ Ω cm). The average optical transmittance of the films was over 90%. The optical bandgap was found to decrease with increasing annealing temperature.     

Preparation and photocatalytic properties of ilmenite NiTiO<Subscript>3</Subscript> powders for degradation of humic acid in water

The powders of ilmenite structure NiTiO₃ were prepared by a modified Pechini process using tetrabutyl titanate and nickel acetate as raw materials, and using citric acid and ethanol as a chelating agent and a solvent respectively. The powder samples were characterized by thermogravimetric and differential thermal analysis (TG-DTA) and X-ray diffraction (XRD). The photocatalytic activity of NiTiO₃ under the irradiation of ultraviolet rays (UV) light was evaluated by degrading humic acid (HA) in water as a probe reaction. The possible photodegradation mechanism was studied by the examination of active species ·OH, ·O₂⁻, and holes (h⁺) through adding scavengers. The TG-DTA and XRD results indicated that the good crystal structure of ilmenite phase NiTiO₃ could be obtained when the Ni-Ti citrate complex was calcined at 600°C. The photocatalytic activity experiments indicated that NiTiO₃ had favourable photocatalytic activity under the irradiation of UV light, and the photocatalytic degradation rate of HA reached 95.3% after a 2.5 h reaction with the photocatalyst calcined at 600°C and a photocatalyst dosage of 0.4 g/L. The possible photocatalytic mechanism was deduced that holes (h⁺) and ·OH radicals are the major reactive active species in the photocatalytic reaction, and dissolved oxygen plays a weak role in the degradation of HA.