Three-dimensional fluorescence characteristics of dissolved organic matter produced by Prorocentrum donghaiense Lu

Filtration and cross-flow ultrafiltration techniques were used to separate culture media of Prorocentrum donghaiense at the exponential growth, stationary and decline stages into < 0.45 mu m filtrate, 100 kDa-0.45 mu m, 10-100 kDa and 1-10 kDa retentate and < 1 kDa ultrafiltrate fractions. The fluorescence. properties of different molecular weights of dissolved organic matter (DOM) were measured by excitation-emission matrix spectra. Protein-like and humic-like fluorophores were observed in the DOM produced by P. donghaiense. The central positions of protein-like fluorophores showed a red shift with prolonged growth duration, shifting from tyrosine-like properties at the exponential growth stage to tryptophan-like properties at the stationary and decline stages. The excitation wavelengths of protein-like fluorophores exhibited some change in the exponential growth and stationary stages with increased molecular size, but showed little change in the decline stage. However, the emission wavelengths in the decline stage exhibited a blue shift. Very distinct C type and A type peaks in humic-like fluorophores were observed. With a prolonged culture time, the intensities of both of the peaks became strong and the excitation wavelengths of peak A showed a red shift, while the A:C ratios fell. More than 94% of fluorescent DOM was in the lower than 1 kDa molecular weight fraction.

Study of a new derivatizing reagent that improves the analysis of amino acids by HPLC with fluorescence detection: application to hydrolyzed rape bee pollen

A simple and sensitive method for evaluating the chemical compositions of protein amino acids, including cystine (Cys)(2) and tryptophane (Try) has been developed, based on the use of a sensitive labeling reagent 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl chloroformate (BCEC-Cl) along with fluorescence detection. The chromophore of the 1,2-benzo-3,4-dihydrocarbazole-ethyl chloroformate (BCEOC-Cl) molecule was replaced with the 2-(11H-benzo[alpha]-carbazol-11-yl) ethyl functional group, yielding the sensitive fluorescence molecule BCEC-Cl. The new reagent BCEC-Cl could then be substituted for labeling reagents commonly used in amino acid derivatization. The BCEC-amino acid derivatives exhibited very high detection sensitivities, particularly in the cases of (Cys)(2) and Try, which cannot be determined using traditional labeling reagents such as 9-fluorenyl methylchloroformate (FMOC-Cl) and ortho-phthaldialdehyde (OPA). The fluorescence detection intensities for the BCEC derivatives were compared to those obtained when using FMOC-Cl and BCEOC-Cl as labeling reagents. The ratios I (BCEC)/I (BCEOC) = 1.17-3.57, I (BCEC)/I (FMOC) = 1.13-8.21, and UVBCEC/UVBCEOC = 1.67-4.90 (where I is the fluorescence intensity and UV is the ultraviolet absorbance). Derivative separation was optimized on a Hypersil BDS C-18 column. The detection limits calculated from 1.0 pmol injections, at a signal-to-noise ratio of 3, ranged from 7.2 fmol for Try to 8.4 fmol for (Cys)(2). Excellent linear responses were observed, with coefficients of > 0.9994. When coupled with high-performance liquid chromatography, the method established here allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids including (Cys)(2) and Try from bee-collected pollen (bee pollen) samples.

Defoliation, nitrogen, and competition: effects on plant growth and resource allocation of Cleistogenes squarrosa and Artemisia frigida

Two species, Artemisia frigida Willd. (C-3, semishrub, and dominant on overgrazed sites) and Cleistogenes squarrosa (Trin.) Keng (C-4, perennial bunchgrass, and dominant or codominant on moderately grazed sites) were studied to determine the effects of defoliation, nitrogen (N) availability, competition, and their interactions on growth, biomass, and N allocation in a greenhouse experiment. The main treatments were: two nitrogen levels (NO = 0 mg N pot(-1), N1 = 60 mg N pot(-1)), two defoliation intensities (removing 60% of total aboveground biomass and no defoliation), and three competitive replacement series (monocultures of each species and mixtures at 0.5:0.5). Our results were inconsistent with our hypothesis on the adaptive mechanisms of A. frigida regarding the interactive effects of herbivory, N, and competition in determining its dominant position on overgrazed sites. Cleistogenes squarrosa will be replaced by A. frigida on over-grazed sites, although C. squarrosa had higher tolerance to defoliation than did A. frigida. Total biomass and N yield and N-15 recovery of C. squarrosa in mixed culture were consistently lower than in monocultures, whereas those of A. frigida grown in mixtures were consistently higher than in monocultures, suggesting higher competitive ability of A. frigida. Our results suggest that interspecific competitive ability may be of equal or greater importance than herbivory tolerance in determining herbivore-induced species replacement in semi-arid Inner Mongolian steppe. In addition, the dominance of A. frigida on overgrazed sites has been attributed to its ability to shift plant-plant interactions through (lap colonization, root niche differentiation, and higher resistance to water stress.

Long-term grazing alters species composition and biomass of a shrub meadow on the Qinghai-Tibet Plateau

Livestock grazing has long been the most widespread land use on the Qinghai-Tibet Plateau, one of the world's highest ecosystems. However, there has been increasing concern during recent decades because of the rapid increase in livestock numbers. To assess the possible influences of grazing on the vast grassland, a long-term grazing experiment in a shrub meadow on the northern Qinghai-Tibet Plateau was carried out. The experiment included five treatments with different stocking rates and one non-grazing (N) treatment. After 17 years of grazing, treatment differences were clear. The species composition differed markedly between grazing intensities, with a decrease in palatable grass species and an increase in unpalatable forbs at higher grazing intensities. The species richness and species diversity, however, were not significantly different between treatments. Vegetation height decreased significantly at higher grazing intensities. Total above,ground biomass declined considerably and the biomass of forbs increased significantly under the higher grazing intensities. The amount of litter was significantly lower under the higher grazing intensities. The results suggest that long-term grazing alters the species composition, vegetation height and biomass production of the alpine grassland ecosystem without significantly changing species richness.

Grazing intensity alters soil respiration in an alpine meadow on the Tibetan plateau

Grazing intensity may alter the soil respiration rate in grassland ecosystems. The objectives of our study were to (1) determine the influence of grazing intensity on temporal variations in soil respiration of an alpine meadow on the northeastern Tibetan Plateau; and (2) characterise, the temperature response of soil respiration under different grazing intensities. Diurnal and seasonal soil respiration rates were measured for two alpine meadow sites with different grazing intensities. The light grazing (LG) meadow site had a grazing intensity of 2.55 sheep ha(-1), while the grazing intensity of the heavy grazing (HG) meadow site, 5.35 sheep ha(-1), was approximately twice that of the LG site. Soil respiration measurements - showed that CO2 efflux was almost twice as great at the LG site as at the HG site during the growing season, but the diurnal and seasonal patterns of soil respiration rate were similar for the two sites. Both exhibited the highest annual soil respiration rate in mid-August and the lowest in January. Soil respiration rate was highly dependent on soil temperature. The Q(10) value for annual soil respiration was lower for the HG site (2.75) than for the LG site (3.22). Estimates of net ecosystem CO2 exchange from monthly measurements of biomass and soil respiration revealed that during the period from May 1998 to April 1999, the LG site released 2040 g CO2 m(-2) y(-1) to the atmosphere, which was about one third more than the 1530g CO2 m(-2) y(-1) released at the HG site. The results suggest that (1) grazing intensity alters not only soil respiration rate, but also the temperature dependence of soil CO2 efflux; and (2) soil temperature is the major environmental factor controlling the temporal variation of soil respiration rate in the alpine meadow ecosystem. (C) 2003 Elsevier Ltd. All fights reserved.

Influence of grazing intensity on performance of perennial grass mixtures in the alpine region of the Tibetan Plateau

Effects of grazing intensity on leaf photosynthetic rate (Pn), specific leaf area (SLA), individual tiller density, sward leaf area index (LAI), harvested herbage DM, and species composition in grass mixtures (Clinelymus nutans + Bromus inermis, Elymus nutans + Bromus inermis + Agropyron cristatum and Elymus nutans + Clinelymus nutans + Bromus inermis + Agropyron cristatum) were studied in the alpine region of the Tibetan Plateau. Four grazing intensities (GI), expressed as feed utilisation rates (UR) by Tibetan lambs were imposed as follows: (1) no grazing; (2) 30% UR as light grazing; (3) 50% UR as medium grazing; and (4) 70% UR as high grazing. Leaf Pn rate and tiller density of grasses increased (P < 0.05), while sward LAI and harvested herbage DM declined (P < 0.05) with the increments of GI, although no effect of GI on SLA was observed. With increasing GI, Elymus nutans and Clinelymus nutans increased but Bromus inermis and Agropyron cristatum decreased in swards, LAI and DM contribution. Whether being grazed or not, Elymus nutans + Clinelymus nutans + Bromus inermis + Agropyron cristatum was the most productive sward among the grass mixtures. Thus, two well-performed grass species (Elymus nutans and Clinelymus nutans) and the most productive mixture of four species should be investigated further as the new feed resources in the alpine grazing system of the Tibetan Plateau. Light grazing intensity of 30% UR was recommended for these grass mixtures when swards, LAI, herbage DM harvested, and species compatibility were taken into account.

Ecological basis of Alpine meadow ecosystem management in Tibet: Haibei Alpine Meadow Ecosystem Research Station

Alpine meadow and shrub are the main pasture types on the Tibetan Plateau, and they cover about 35% of the total land area. In order to understand the structural and functional aspects of the alpine ecosystem and to promote a sustainable animal production system, the Haibei Alpine Meadow Research Station was established in 1976. A series of intensive studies on ecosystem structure and function, including the energy flow and nutrient cycling of the ecosystem, were the main tasks during the first 10 years. Meanwhile, studies with 5 different grazing intensities on both summer and winter pasture have been conducted. In the early years of the 1990s, the research station started to focus its research work on global warming, biodiversity and sustainable animal production systems in pastoral areas. Various methods for improving degraded pasturelands have been developed in the region.

中国北方风成堆积的风化作用与环境变迁—U-Th、~(10)Be及元素地球化学的研究

The surface of the Earth is continuously undergoing changes as a result of weathering-erosion, plate tectonics and volcanic processes. Continental weathering-erosion with its complex rock-water interactions is the central process of global biochemical cycling of elements, and affects the long-term ocean atmosphere budget of carbon dioxide both through the consumption of carbonic acid during silicate weathering and through changes in the weathering and burial rates of organic carbon. Rates of the weathering-erosion depend on a variety of factors, in particular rock properties and chemical composition, climate (especially rainfall), structure, and elevation. They are quite variable on a regional scale. Thus, environmental changes in a region could be indicated by the history of weathering-erosion in the region. Recent attention has focused on increased silicate weathering of tectonically uplifted areas in the India-Asia collision zone as a possible cause for falling atmospheric CO_2 levels in the Cenozoic era. The wind blown dust deposits in the Loess Plateau is derived from the arid and semiarid regions in northwestern China, in turn, where the deposits have been derived from the Qinghai-Xizang Plateau and the high mountains around. Therefore, geochemistry of the wind blown loess-paleosol and red clay sequences may provide insight both to paleoenvironmental changes on the Loess Plateau, and to the uplift and weathering-erosion histories of the Qinghai-Xizang Plateau. In this paper, uranium-thorium series nuclides and cosmogenic ~(10)Be have been employed as tracers of weathering intensities and histories of the dust sediments in the Loess Plateau. Major elements, such as Na, Al, Fe etc., are also used to estimate degree of chemical alteration of the dust sediments and to rebuild the history of weathering on the Loess Plateau. First of all, using a low-level HPGe γ-ray detector, we measured U and Th series nuclides in 170 loess and paleosol samples from five sites in the Loess Plateau, going back 2.6 Ma. The results show that ~(238)U activities are disequilibrium with its daughter nuclide ~(230)Th in young loess-paleosol sequence, indicating that weathering was happened both in dust deposition site and in dust source regions. Using concentrations of ~(238)U and ~(232)Th in the samples, we estimated the amounts of ~(238)U leached out of from paleosols due to weathering. Further, based on analyses of ~(230)Th in paleosols deposited in the past ca. 140 ka, we determined when the paleosols weathered in the source regions. We conclude that most of the weathering in the dust-source regions may have occurred during the interglacials before dust deposition.

柴达木盆地北缘地区油气成藏过程模拟与含油气系统评价

As an important part of petroleum exploration areas in the west of China, the north part of Qaidam basin is very promising in making great progress for petroleum discovery. But there are still many obstacles to overcome in understanding the process of petroleum formation and evaluation of oil & gas potential because of the complexity of geological evolution in the study area. Based upon the petroleum system theory, the process of petroleum formation is analyzed and the potential of oil & gas is evaluated in different petroleum systems by means of the modeling approach. The geological background for the formation of petroleum systems and the consisting elements of petroleum systems are described in detail. The thickness of strata eroded is estimated by means of vitrinite reflectance modeling, compaction parameter calculating and thickness extrapolating. The buried histories are reconstructed using the transient compaction model, which combines of forward and reverse modeling. The geo-history evolution consists of four stages - sedimentation in different rates with different areas and slow subsidence during Jurassic, uplifting and erosion during Cretaceous, fast subsidence during the early and middle periods of Tertiary, subsidence and uplifting in alternation during the late period of Tertiary and Quaternary. The thermal gradients in the study area are from 2.0 ℃/100m to 2.6 ℃/100m, and the average of heat flow is 50.6 mW/m~2. From the vitrinite reflectance and apatite fission track data, a new approach based up Adaptive Genetic Algorithms for thermal history reconstruction is presented and used to estimate the plaeo-heat flow. The results of modeling show that the heat flow decreased and the basin got cooler from Jurassic to now. Oil generation from kerogens, gas generation from kerogens and gas cracked from oil are modeled by kinetic models. The kinetic parameters are calculated from the data obtained from laboratory experiments. The evolution of source rock maturation is modeled by means of Easy %Ro method. With the reconstruction of geo-histories and thermal histories and hydrocarbon generation, the oil and gas generation intensities for lower and middle Jurassic source rocks in different time are calculated. The results suggest that the source rocks got into maturation during the time of Xiaganchaigou sedimentation. The oil & gas generation centers for lower Jurassic source rocks locate in Yikeyawuru sag, Kunteyi sag and Eboliang area. The centers of generation for middle Jurassic source rocks locate in Saishenteng faulted sag and Yuka faulted sag. With the evidence of bio-markers and isotopes of carbonates, the oil or gas in Lenghusihao, Lenghuwuhao, Nanbaxian and Mahai oilfields is from lower Jurassic source rocks, and the oil or gas in Yuka is from middle Jurassic source rocks. Based up the results of the modeling, the distribution of source rocks and occurrence of oil and gas, there should be two petroleum systems in the study area. The key moments for these two petroleum, J_1-R(!) and J_2-J_3, are at the stages of Xiaganchaigou-Shangyoushashan sedimentation and Xiayoushashan-Shizigou sedimentation. With the kinetic midels for oil generated from kerogen, gas generated from kerogen and oil cracked to gas, the amount of oil and gas generated at different time in the two petroleum systems is calculated. The cumulative amount of oil generated from kerogen, gas generated from kerogen and gas cracked from oil is 409.78 * 10~8t, 360518.40 * 10~8m~3, and 186.50 * 10~8t in J_1-R(!). The amount of oil and gas generated for accumulation is 223.28 * 10~8t and 606692.99 * 10~8m~3 in J_1-R(!). The cumulative amount of oil generated from kerogen, gas generated from kerogen and gas cracked from oil is 29.05 * 10~8t, 23025.29 * 10~8m~3 and 14.42 * 10~8t in J_2-J_3 (!). The amount of oil and gas generated for accumulation is 14.63 * 10~8t and 42055.44 * 10~8m~3 in J_2-J_3 (!). The total oil and gas potential is 9.52 * 10~8t and 1946.25 * 10~8m~3.

黄土高原粉尘堆积源区环境及风化历史初步研究

In this study, we examined the surface features of quartz grains, the quartz oxygen isotopic ratios and the mineralogical compositions of the loess - paleosol - red clay sediments systematically. The surface features of quartz grains do not show significant changes of the dust deposits through the past seven million years. The particles were mainly created in the process of glacial and frost weathering of high mountains. Then the surfaces were altered in some degree by the flood and wind abrasion. The surface features registered all these processes. The assemblages of surface features changed for four times in the past seven million years, the occurrence ages are: 5.0~4.2MaBP, about 3.6MaBP, about 2.6MaBP and about 0.9MaBP, respectively. This may indicate that there were uplift events of the Tibetan Plateau during those times. The oxygen isotopic compositions of quartz in the sediments represent the oxygen isotopic compositions of the initial dusts because of the stable properties of quartz both physically and chemically. The oxygen isotopic compositions of 4~16um quartz changed significantly at about 2.6MaBP, decreasing from about 19.5%o to about 18.5%o. This decrease of quartz oxygen isotopic ratio suggests that the environments of the dust source areas changed at that time, or the range of dust source area changed at that time. The environmental change may result from the structural evolution of the Tibetan Plateau and global cooling at that time. The coarse fractions (>30μm) of the dust deposits were examined using the EDXA device for mineral identification. The quartz content has a decrease trend during 7~2MaBP, then increase rapidly at about 2MaBP. After 2MaBP, quartz content continues to decrease. The Ca-plagioclase content / quartz content ratio increase at about 3.6MaBP. The ratio shows a peak of 3-6 fold values at about 2.5~1.8MaBP, the cause of this is still unknown. The Ca-plagioclase content / quartz content ratio continues to increase after 1 MaBP. The flowing can be regarded as the conclusion remarks of this study: Some of the red clay sediment of the Chinese Loess Plateau (at least Lingtai and Jingchuan red clays) is eolian in origin. The quartz grains from dust deposits throughout the past seven million yeas showed the clues of glacial and frost processes. This indicates that the high mountains of western China reached a certain altitude to favor the glacial and/or frost processes at least seven millions years before. The weathering intensities of the past seven nnillion yeas have a decreasing trend. In about 5~4.5MaBP, the weathering is relatively weak, and the dust supply is relatively low. At about 3.6MaBP and 2.6MaBP, the dust supply increased significantly. The mineralogical composition, the quartz surface feature and the quartz oxygen isotope composition were influenced by the uplift of the Tibetan Plateau. The Plateau may have reached a certain altitude to generate the arid regions of inland China and favor the glacial and frost weathering. And it underwent a phased uplift, which have uplift events at about 3.6MaBP and 2.6MaBP.

西北太平洋某海域40ka来的地磁场相对强度研究

Paleointensity changes of geomagnetic field help us to understand the evolutionprocess of earth completely and provide further constraints for earth interior process and geodynamo model. Marine sediments are good carriers for relative paleointensity of geomagnetic field. But in most cases, deep sea sediments that conform with magnetic "uniformity" usually have low sedimentation rate about l-2cm/ka and lie under the Carbonate Compensate Depth with little carbonate content. Therefore, the number of relative paleointensity records with detailed oxygen stratigraphy is still rare. This thesis focus on four cores from east of Ryukyu Trench which have foraminiferal content of 5-30% and sedimentation rate of lOcm/ka and wish to get centennial -millennial changes of relative paleointensity.The sediments from east of Ryukyu Trench conform with magnetic "uniformity" and remanences of four cores all show single component with stable direction and faithfully record the magnetic field. The NRM301T1T/ARM and NRMsomT/ x are still affected by grain size and concentration changes although the sediments are "uniform" , indicating the uniformity might not enough for relative paleointensity. After renomalized by grain size parameter MDF, the intensities remove the effect of grain size changes to different degrees and show coherency in 1-1 Oka scale with results from ODP983/984. The characteristics of paleointensity of geomagnetic field arefrom 32-24kaBP, paleointensity of geomagnetic field is low;24-12kaBP, paleointensity of geomagnetic field is high and shows two peaks boundary with 19kaBP.3) 12-5.3ka, paleointensity is low. Then increase from 5,3kaBP until a small trough at 2.7kaBP, then increase till now.

Formation of the V center on H-type zeolites with thermal treatment

The effect of thermal treatment on H-MCM-22 and H-ZSM-5 zeolites was investigated using the electron spin resonance technique. A six-line signal (denoted as A, g = 2.048, A = 22. 15 G) was detected on H-MCM-22 after He purging at high temperatures, whose intensities increased with the treating temperature. The same signal was also found on H-ZSM-5 zeolites with different crystal sizes. The paramagnetic center was identified as a V center, namely, a hole of an electron trapped on an oxygen atom bonding to a nearby aluminum atom. These signals appeared only on a dealuminated sample or a sample concomitantly with dealumination. The formation of the hole might involve an electron transferring from the lattice oxygen to a nonframework aluminum species, and the hyperfine splitting is caused by the interaction between the electron hole locating on the p orbit of oxygen and the framework aluminum bonding with the oxygen. The signal disappeared after the sample was exposed to air or oxygen at room temperature. However, the process was reversible. A new set of signals (denoted as B, g(1) = 2.008, g(2) = 2.003, g(3) = 1.9985) was observed after oxygen adsorption on the H-MCM-22 pretreated with He at 973 K or He purging at 973 K on the H-MCM-22 pretreated with oxygen at 813 K, which was attributed to the O- species.

Formation and dissociation of protonated pyridine-methanol cluster ions at 355 and 266 nm

The multi-photon ionization process of the hydrogen-bond cluster of pyridine-methanol has been investigated using a conventional and reflectron time-of-flight mass spectrometer (RTOF-MS) at 355 and 266 nm laser wavelengths, respectively. The sequences of the protonated cluster ions (CH3OH)(n)H+ and (C5H5Nn)(CH3OH)(m)H+ (n = 1,2) were observed at both laser wavelengths, while the sequence of the cluster ions (CH3)OHn (H2O)H+ was observed only at 355 nm laser wavelength. The difference between the relative signal intensities of the protonated methanol cluster ions at different laser wavelengths is attributed to different photoionization mechanisms. Some nascent cluster ions in metastable states dissociated during free flight to the detector. The dissociation kinetics is also discussed. (C) 2000 Elsevier Science B.V.

A combined DFT and SCRF study of solvent effects on 4-methyl-3-penten-2-one

The IR spectrum of 4-methyl-3-penten-2-one is interpreted with the aid of normal coordinate calculations within the Onsager self-consistent reaction field (SCRF) model, using a density functional theory (DFT) method at the Becke3LYP/6-31G* level. The solvent effects on the geometry, energy, dipole moment, and vibrational frequencies of 4-methyl-3-penten-2-one in the solution and in the liquid phase are calculated using the Onsager SCRF model. The calculated vibrational frequencies in the liquid-phase are in good agreement with the experimental values. The solvent reaction field has generally weak influence. For the two main bands of C=C and C=O mixed vibrational modes, small frequency shifts (5-6 cm(-1)), but relatively large changes in IR intensities (up to 101 km mol(-1) in the liquid phase) are found. (C) 1999 Elsevier Science BV. All rights reserved.

Using oxidized carbon nanotubes as matrix for analysis of small molecules by MALDI-TOF MS

Oxidized carbon nanotubes are tested as a matrix for analysis of small molecules by matrix assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS). Compared with nonoxidized carbon nanotubes, oxidized carbon nanotubes facilitate sample preparation because of their higher solubility in water. The matrix layer of oxidized carbon nanotubes is much more homogeneous and compact than that of nonoxidized carbon nanotubes. The efficiency of desorption/ionization for analytes and the reproducibility of peak intensities within and between sample spots are greatly enhanced on the surface of oxidized carbon nanotubes. The advantage of the oxidized carbon nanotubes in comparison with alpha-cyano-4-hydroxycinnamic acid (CCA) and carbon nanotubes is demonstrated by MALDI-TOF-MS analysis of an amino acid mixture. The matrix is successfully used for analysis of synthetic hydroxypropyl P-cyclodextrin, suggesting a great potential for monitoring reactions and for product quality control. Reliable quantitative analysis of jatrorrhizine and palmatine with a wide linear range (1-100 ng/mL) and good reproducibility of relative peak areas (RSD less than 10 %) is achieved using this matrix. Concentrations of jatrorrhizine (8.65 mg/mL) and palmatine (10.4 mg/mL) in an extract of Coptis chinensis Franch are determined simultaneously using the matrix and a standard addition method. (c) 2005 American Society for Mass Spectrometry.