1MAS NMR spectra of kao linite/formamide intercalation compound

The high spinning speed 1H magic angle spinning nuclear magnetic resonance (1H MAS NMR) technique was employed to distinguish the two groups of surface hydroxyls of kaolinite and investigate the intercalation mechanism of kaolinite/formamide compound. The proton chemical shifts of the inner hydroxyl and inner surface hydroxyl of kaolinte are in the range of δ-1.3-0.9 and δ 2.4-3.0 respectively. After formamide intercalation three proton peaks were detected. The proton peak of the inner surface hydroxyls of the intercalation compound shifts to high-field with δ 2.3-2.7, which is assigned to the formation of the hydrogen bond between the inner surface hydroxyl and formamide carbonyl group. Whereas, the proton peak of the inner hydroxyl shifts to δ-0.3 toward low-field, that is attributed to van der Waal's effect between the inner hydroxyl proton and the amino group proton of the formamide which may be keyed into the ditrigonal hole of the kaolinite. The third peak, additional proton peak, is in the range of δ5.4-5.6, that is ascribed to the hydrogen bond formation between the amino group proton of formimide and SiO4 tetrahedral oxygen of the kaolinite.     

1H MAS NMR spectra of hydroxyl species on diatomite surface

High spinning speed¹H magic-angle spinning nuclear magnetic resonance (¹H MAS NMR) was used to detect surface hydroxyl groups of diatomite, which include isolated hydroxyl groups and hydrogen-bonded hydroxyl groups, and water adsorbed on diatomite surface that include pore water and hydrogen-bonded water. The corresponding proton chemical shifts of above species are ca. 2.0, 6.0–7.1, 4.9 and 3.0 respectively. Accompanied by thermal treatment temperature ascending, the pore water and hydrogen-bonded water are desorbed successively. As a result, the relative intensities of the peaks assigned to protons of isolated hydroxyl groups and hydrogen-bonded hydroxyl groups increase gradually and reach their maxima at 1000°C. After 1100°C calcination, the hydroxyl groups that classified to strongly hydrogen-bonded ones and the isolated hydroxyl groups condense basically. But some weakly hydrogen-bonded hydroxyl groups may still persist in the micropores.     

Resonance-enhanced multiphoton ionization spectroscopy on the B′2Σ+ and B2Π states of NS

Resonance-enhanced multiphoton ionization （REMPI） spectra of N^32S and N^34S have been recorded in the range of 35700-40200 cm^-1. The radical was generated by a pulsed dc discharge of a mixture of SF6 and N2 under a supersonic free jet condition. All the 16 observed bands of N^32S radicals have been assigned, among which 12 bands belong to three transition progressions （v′=0-4, 0）, （v′=1-4, 1） and （v′=2-4, 2） from the X^2П ground state to the B′^2∑^＋ upper state and the rest correspond to （9, 0）, （10, 0）, （11, 0） and （12, 0） bands of B^2П-X^2П transition, respectively. Analysis of the rotationally resolved spectra yields exhaustive spectroscopic constants of both the X^2П ground state and the B′^2∑^＋ excited state. The electronic transition bands of the isotopic molecule N^34S have been rotationally analyzed for the first time and the rotational constants of the ground and upper states have been determined simultaneously.     

Effects of Yb^3＋ codoping on visible and near infrared emissions of Er^3＋-Yb^3＋ codoped Al2O3 powders by the sol-gel method

The 0.1 mol% Er^3＋ and 0-2 mol% Yb^3＋ codoped Al2O3 powders were prepared by the sol-gel method, and the phase structure, including only two crystalline types of doped Al2O3 phase, γ-（Al,Er, Yb）2O3 and θ-（Al,Er, Yb）2O3, was detected at the sintering temperature of 1000℃. The visible and near infrared emissions properties depended strongly on the Yb^3＋ codoping, and the corresponding maximal peak intensities centered at about 523, 545, 660 and 1533 nm were obtained respectively for the 0.1 mol% Er^3＋ and 0.5 mol% Yb^3＋ codoped Al2O3 powders, which were composed of θ-（Al,Er,Yb）2O3 and a small amount of γ-（Al,Er, Yb）2O3 phases. The two-photon absorption process was responsible for the visible up-conversion emissions, and the one-photon absorption process was involved in the near infrared emissions of the Er^3＋-yb^3＋ codoped Al2O3 powders.     

Export and remineralization of POM in the Southern Ocean and the South China Sea estimated from 210Po/210Pb disequilibria

Disequilibria between ^210Po and ^210Pb in the upper water and their potential applications as a proxy of particle export and remineralization were examined in the Southern Ocean （station IV3） and the South China Sea （NS44）. ^210po was deficit in surface waters but excessive relative to ^210Pb in subsurface waters. Good positive correlation between ^210Po and particulate organic carbon （POC） indicated deficits and excess of ^210Po resulted from particulate organic matter （POM） export and remJneralization respectively, which was also supported by the decreased δ^13C and increased δ^15N downwards as a result of particle remineralization. On the basis of ^210Po/^210Pb box-model, POC export flux out of the surface waters were 1.2 mmol C. m^-2. d^-1 and 2.3 mmol C. m^-2. d^-1 for station NS44 and IV3, respectively. In the subsurface waters, remineralization fluxes of ^210Po were 0.062 Bq. m^-2.d^-1 and 0.566 Bq.m^-2.d^-1 for station NS44 and IV3 along with the recycle efficiency of 52±26% and 119±52%, respectively. Remineralized fluxes of POM derived from ^210Po and exported POC were 0.6 mmol C.m^-2.d^-1 and 2.7 mmol C. m^-2. d^-1 for NS44 and IV3. This study suggested that ^210Po was a powerful tracer of particle export and remineralization.     

The seasonal variations of δ~(18)O , Cl~- , Na~+ , NO_3~- and Ca~(2+) in the snow and firn recovered from Princess Elizabeth Land, Antarctica

Snow and firn samples recovered from two snow pits (2.5 and 4.5m deep) and one 50-m firn core along the route of the 1996/1997 Chinese First Antarctic Inland Traverse Expedition in Princess Elizabeth Land, East Antarctica, have been measured for chemical composition and oxygen isotope ratio. In the two snow pits, the variations of NO3- are partly in phase with that of δ18O, while the variations of Cl~ and Na+ are in inverse phase with that of δ18O. The variations of CI- , Na+ , NO3- and δ18O show obvious seasonal variations and annual stratag-raphy. However, with the depth increasing, the seasonal variations of δ18O are gradually smoothed below 3 m (corresponding to about 10-year mass accumulation) in depth while the seasonal variations of Cl- , Na+ and NO3- are kept fairly well in the whole profile of the 50-m firn core (corresponding to about 250-year mass accumulation). The results provide a useful tool for dating the snow stratum in this region. On the contrary, no obvious seasonal variations of Ca2 + are found in the profiles.     

<Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar isochron ages of lawsonite blueschists from Jiuquan in the northern Qilian Mountain,NW China,and their tectonic implications

Using laser ⁴⁰Ar/³⁹Ar dating method, we have gotten the metamorphic ages of lawsonite blueschist and epidote blueschist from Jiuquan, northern Qilian Mountain, NW China. The high quality laser ⁴⁰Ar/³⁹Ar dating of glaucophane from lawsonite blueschist gives an isochron age of 413±5 Ma. The isochron age obtained from phengite in epidote blueschist is 415±7 Ma. These data, combining with peak metamorphic P-T conditions and regional geological setting, allow us to infer that the lower limit of the ages of the prograde subduction metamorphism from lawsonite blueschist facies to epidote blueschist facies occurred at ca. 413–415 Ma, which also suggests that the formation of lawsonite blueschist in the northern Qilian Mountain maybe resulted from the corner flow in the cold subduction zone. This study shows that the final closing time of the northern Qilian remnant oceanic basin is about 413–415 Ma, which also represents the convergent age between the North China Craton and the Qaidam block.     

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.     

Determination of trophic relationships within a Bohai Bay food web using stable δ15N and δ13C analysis

This study measured stable carbon and nitrogen isotope ratios in phytoplankton, zooplankton, five invertebrates species, eight fishes species and three seabirds species collected in Bohai Bay. δ^13C ranged from -25.38‰ to -11.08‰ showing a relative low enrichment in the food web from Bohai Bay. The mean δ^13C of mullet is higher than that of other organisms, and this might be due to that mullet is migration fish and feeds mainly on inshore sources. δ^15N ranged from 4.08‰ to 13.98‰, and showed a step-wise enrichment with trophic level of 3.8‰. The δ^15N enrichment factor was used to construct an isotopic food web model to establish trophic relationships within this marine food web. According to this model, exact trophic levels of all organisms were estimated as 1.46-2.10, 1.91-3.32, 2.55-4.23 and 2.98-4.28 for plankton, invertebrates, fishes, and seabirds.     

Theoretical study on the lithium bond interaction of furan homologues C4H4Y （Y=O,S） with LiCH3 via DFT and MP2

The optimizations geometries and interaction energy corrected by BSSE of the complexes between C4H4Y （Y=O, S） and CHiLi have been calculated at the B3LYP/6-311＋＋G^＊＊ and MP2/6-311＋＋G^＊＊ levels. Three complexes were obtained. Abnormally, the calculations showed that all the C10--Li14 bond lengths increased obviously but the blue-shift of C10-Li14 stretching frequency occurred after formed complexes. The calculated binding energy with basis set super-position error （BSSE） and zero-point vibrational energy corrections of complexes I-III is -45.757, -35.700 and -39.107 kJ·mol^-1, respectively. The analyses on the combining interaction with the atom-in-molecules theory （AIM） also showed that a relatively strong lithium bond interaction presented in furan homologues C4H4Y-LiCH3 systems. Natural bond orbital theory （NBO） analysis has been performed, and the results revealed that the complex I is formed with n-σ type lithium bond interaction between C4H40 and LiCH3, complex II is formed with TT-s type lithium bond interaction between C4H4O and LiCH3, and complex III is formed with TT-s and n-s type lithium bond interactions between C4H4S and LiCH3, respectively.     

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.     

Preliminary study of microscale zircon oxygen isotopes for Dabie-Sulu metamorphic rocks： Ion probe in situ analyses

151 in situ analyses of oxygen isotopes were carried out by ion micro-probe for zircons from 8 localities of HP-UHP metamorphic rocks including eclogites in the Dabie-Sulu terrane. The results show significant heterogeneity in δ^18O values, with variation in different rocks from -8.5‰ to 9.7‰ and within one sample from 2‰ to 12‰. No measurable difference in δ^18O was observed between protolith magmatic (detrital) zircons and metamorphic recrystallized zircons within analytical uncertainties from the ion micro-probe measurements. This indicates that the metamorphic zircons have inherited the oxygen isotopic compositions of protolith zircons despite the HP to UHP metamorphism. According to their protolith ages from zircon U-Pb in situ dating by the same ion micro-probe, two groups of oxygen isotope composition are recognized, with one having δ^18O values of 6‰-7‰ for old protolith of 1.9-2.5 Ga ages and the other 0‰-2‰ for young protolith of 0.7-0.8 Ga ages. The latter anomalously low δ^18O values of zircons indicate that the magma has had the obvious involvement of meteoric water when forming the young protolith of high-grade metamorphic rocks. This may be correlated with the snowball Earth event occurring in South China and the world elsewhere during the Neoproterozoic.     

Potash-rich volcanic rocks and lamprophyres in western Shandong Province: 40Ar-39Ar dating and source tracing

Highly precise ⁴⁰Ar-³⁹Ar dating results demonstrate that the ages of potash-rich volcanic rocks in western Shandong Province are 114.7–124.3 Ma, and that of the lamprophyres is 119.6 Ma. The potash-rich volcanic rocks have relatively high (⁸⁷Sr÷⁸⁶Sr)_i ratios (0.708715–0.711418) and distinctly negative ε_nd values (−11.47–−17.54), and are enriched in radiogenic lead (²⁰⁶Pb÷²⁰⁴Pb=17.341−17.622, ²⁰⁷Pb÷²⁰⁴Pb=15.525−15.538, ²⁰⁸Pb÷²⁰⁴Pb = 37.563−37.684). Similarly, the lamprophyres also have quite low ε_nd values (−11.57–−19.64). Based on the fact that the Sr, Nd and Pb isotopic compositions of potash-rich volcanic rocks are very consistent with that of the clinopyroxene separates, and by integrating comprehensive analyses of their tectonic settings, and extensive comparisons of the Sr, Nd isotopic compositions with that of the related simultaneous rocks, it is concluded that the potash-rich volcanic rocks and lamprophyres in western Shandong Province were most possibly derived from the partial melting of enriched mantle which was caused by source contamination and metasomatism of subducted continental crustal materials.     

Carbon isotopic composition,turnover and origins of soil CO<Subscript>2</Subscript> in a monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir,South China

Carbon isotopic compositions of soil CO2 in rainy season (July) from two natural soil profiles (DHLS & DHS) in the monsoon evergreen broadleaf forest in the Dinghushan Biosphere Reservoir (DBR), South China, are presented. Turnover and origins of soil CO₂ are preliminarily discussed in this paper. Results show that the content of soil CO2 varies between 6120 and 18718 ppmv, and increases with increasing depth until 75 cm, and then it declines. In DHLS, soil CO₂ δ¹³C ranges from −24.71‰ to −24.03‰, showing a significant inverse correlation (R²＝0.91) with the soil CO₂ content in the same layer. According to a model related to soil CO₂ δ¹³C, the soil CO₂ is mainly derived from the root respiration (>80%) in DHLS. While in DHS, where soil CO₂ ? 13C ranges from −25.19‰ to −22.82‰, soil CO₂ is primarily originated from the decomposition of organic matter (51%–94%), excluding the surface layer (20 cm, 90%). Radiocarbon data suggest that the carbon in soil CO₂ is modern carbon in both DHLS and DHS. Differences in ¹⁴C ages between the “oldest” and “youngest” soil CO₂ in DHLS and DHS are 8 months and 14 months, respectively, indicating that soil CO₂ in DHLS has a faster turnover rate than that in DHS. The ¹⁴C values of soil CO₂, which range between 100.0‰ and 107.2‰ and between 102.5‰ and 112.1‰ in DHLS and DHS, respectively, are obviously higher than those of current atmospheric CO₂ and SOC in the same layer, suggesting that soil CO₂ is likely an important reservoir for Bomb-¹⁴C in the atmosphere.     

Soil erosion rates and characteristics of typical alpine meadow using <Superscript>137</Superscript>Cs technique in Qinghai-Tibet Plateau

Alpine meadow is the predominant ecosystem in Qinghai-Tibet Plateau.The firm turf of alpine meadow formed by sub-surface anfractuous roots can be effective in conserving water and soil.Alpine meadow is a primary contributor to the Chinese Water Tower.For quantitative assess anti-erosion ability of alpine meadow,this paper selected three typical meadow slopes with>60% vegetation coverage to evaluate soil erosion rates using 137Cs.The results showed that(1)soil erosion intensity of typical alpine meadow was slight to light.Erosion rates were 464 t km–2 a–1 in Malong Village,415 t km–2 a–1 in Yeniugou Town and 875 t km–2 a–1 in Zhenqin Town respectively;(2)soil erosion rates were correlated negatively with vegetation coverage,and the relationship was clearer at the slope scale than plot scale;(3)the relationship between soil erosion and vegetation coverage showed that vegetation coverage was a predominant factor in retaining soil and water on slopes.With complete turf and high vegetation coverage, alpine meadow was of great significance for soil conservation and prevention of soil erosion.     

Surface tension and specific heat of liquid Ni<Subscript>70.2</Subscript>Si<Subscript>29.8</Subscript> alloy

The thermophysical properties of liquid alloys in me-tastable state are of importance for liquid-solid phase transformation under nonequilibrium conditions[1―10]. Sur-face tension and specific heat, two of the most important thermophysical properties, have significant influences on the process of crystal nucleation and growth. Furthermore, it is necessary to obtain these data so as to perform quan-titative research on rapid solidification[3―10]. The tradi-tional measurement methods, however,…     

Southwest monsoon changes indicated by oxygen isotope of ostracode shells from sediments in Qinghai Lake since the late Glacial

The δ 18O records of ostracode shells in sediments of core QH-2000 from Qinghai Lake can be used as a better proxy to reflect monsoon changes. Low monsoon precipitation between 17.5 and 11 cal. ka BP is indicated by positive δ 18O values averaging 2.37‰. A fast shift in δ 18O from positive at 11 cal. ka BP to negative at 10 cal. ka BP indicates sharp increase of monsoon precipitation. An interval of generally high monsoon precipitation is observed between 10 and 6 cal. ka BP with δ 18O values averaging -2.15‰. Decrease of monsoon precipitation between 6 and 2.5 cal. ka BP is indicated by positive δ 18O values. δ 18O keeps positive values averaging 3.0‰ between 2.5 and 0 cal. ka BP suggesting low high monsoon precipitation. The climatic changes indicated by δ 18O records of ostracode shells in sedi- ments of core QH-2000 from Qinghai Lake and our broader regional comparison show that the climate in Qinghai Lake since the late Glacial is probably controlled by southwest monsoon other than southeast monsoon.     

Oxygen isotope variation in the water cycle of the Yamzho lake Basin in southern Tibetan Plateau

Given the potential use of stable isotope in the paleoclimate reconstruction from lacustrine records as well as in the local hydrology cycle, it is crucial to understand the processes of stable isotope evolution in catchment in the Tibetan Plateau region. Here we present a detailed study on the water oxygen isotope based on 2 years observation including precipitation, river water and lake water in the Yamzho Lake, south of the Tibetan Plateau. Temporal variation of local precipitation 5180 shows an apparent ＂monsoon cycle＂. In monsoon season, 5180 in waters is lower. In non-monsoon season, δ^18O in precipitation and lake water is higher and higher river δ^18O exists in spring, probably reflecting the effect of land surface evaporation, together with the higher δ^18O values in spring precipitation. It is also found that the surface lake water δ^18O varies seasonally and annually. The lower lake water δ^18O in the late summer is apparently related to the summer monsoon precipitation. The mean δ^18O value of lake water in 2007 is 1.2‰ higher than that in 2004, probably due to the less monsoon precipitation in summer of 2007, as can be confirmed from the precipitation data at the Langkazi meteorological data. It is also found that an obvious shift of vertical lake water δ^18O reflects the fast mixture of lake water. δ^18O values of lake water are over 10‰ higher than those of precipitation and river water in this region due to the evaporation fractionation. The modeled results show that the evaporation process of the lake water is sensitive to relative humidity, and the present lake water δ^18O reflects a relative humidity of 51% in the Yamzho Lake. It shows that the lake will take 30.5 years to reach present lake water δ^18O given a large shift in the input water δ^18O. The modeled results also reveal that surface lake water temperature and inflow δ^18O have slight effect on the isotopic balance process of lake water in the Yamzho Lake.     

Synoptic-scale variation of δ18O in summer monsoon rainfall at Lijiang, China

Based on the daily δ~(18)O data in June―September 2003 at Lijiang and the daily mean NCEP/ NCAR reanalysis data, synoptic-scale variation of δ~(18)O in summer monsoon rainfall was investigated. The 'precipitation amount effect' is obvious for the daily δ~(18)O variation, whereas the 'temperature effect' is insignificant. Alternate occurrences of active phase and break phase of the southwest monsoon probably influence the synoptic-scale δ~(18)O variation prominently. Moreover, the isotopic composition in precipitation during the late monsoon months is presumably influenced significantly by recycling of monsoon precipitation. Both the above factors disturb the 'amount effect' of isotopic variation in the monsoon region. This study also indicates that the synoptic-scale rainfall δ~(18)O variation at Lijiang in summer is domi-nated by the Indian monsoon depression (low pressure) system at large scale. These results are important for further studying the 'amount effect' and reconstructing paleoclimate in the monsoon region.     

Study of altitudinal lapse rates of δ18O in precipitation/river water with seasons on the southeast Tibetan Plateau

Seasonal δ^18O variation in water on the southeast Tibetan Plateau has been studied, showing the consistent variation pattern of δ^18O with altitude indicative of relevant atmospheric circulation processes. Study shows a similar variation pattern of fixed-site river water δ^18O with that of the precipitation δ^18O in southeast Tibet. δ^18O in regional rivers in southeast Tibet demonstrates a gradual depletion with increasing altitude, though the rates vary seasonally. The most depleted river ^18O occurs during the monsoon period, with the lowest δ^18O/altitude lapse rate. The river ^18O during the westerly period is also depleted, together with low δ^18O/altitude lapse rate. The pre-monsoon rivers witness the most enriched ^18O with least significant correlation coefficient with the linear regression, whilst the postmonsoon rivers witness the largest δ^18O/altitude lapse rate. Different coherence of seasonal δ^18O variation with the altitude effect is attributed to different moisture supplies. Though sampling numbers vary with seasons, the δ^18O-H linear correlation coefficients all reach the 0.05 confidence level, thus witnessing the variation features of δ^18O in seasonal river water due to the influence of atmospheric general circulation and land surface processes revealed from the altitudinal lapse rates.