Determination of Hf–Sr–Nd isotopic ratios by MC-ICP-MS using rapid acid digestion after flux-free fusion in geological materials

In this study, we established a rapid acid digestion for determining Hf-Sr-Nd isotopic ratios of geological samples by using MC-ICP-MS. Conditions of 1600 ℃ for 1 min and 1400 ℃ for 1 min were adopted for fusing intrusive rocks and extrusive rocks, respectively. The rapid acid digestion technique is superior in digestion time compared with high-pressure PTFE bomb method. The procedural blanks of the method were also lower than that flux fusion. Replicate analyses of international certified reference materials （CRMs） indicate that isotopic ratios of ^176Hf/^177Hf, ^87Sr/^86Sr and 143Nd/144Nd agree well with previously published data. The external reproducibility （2SD, n = 5） of ten CRMs are ±0.000030 for ^87Sr/^86Sr, ± 0.000030 for ^143Nd/^144Nd, and ±0.000018 for ^176Hf/^177Hf.

Carbon isotope ratios of n-alkanoic acids: new organic proxies for paleo-productivity in Antarctic ponds

Primary productivity in the Antarctic aquatic environment with simple ecosystems is sensitive to climate and environmental fluctuations.We investigatedδ13C values for n-alkanoic acids derived from phototrophic organisms in a lacustrine sediment core(IIL3)to indicate primary productivity in ponds on Inexpressible Island in the western Ross Sea,Antarctica.Short-chain n-alkanoic acids(C14–C18)were abundant in the IIL3 sediment profile.The carbon isotope ratios of short-chain n-alkanoic acids in the sediment samples and floating microbial mats were similar,indicating that the short-chain n-alkanoic acids in the IIL3 sediment profile predominantly originated from phototrophic organisms.Theδ13C values for the short-chain n-alkanoic acids varied widely through the sediment profile,and 13C-enrichment of n-alkanoic acids was most likely related to high productivity due to carbon-limited conditions caused by enhanced photosynthetic efficiency.Theδ13C values for the n-alkanoic acids changed over the past 3200 years in similar ways to organic proxies for aquatic productivity(n-alkanoic acid and sterol sedimentary fluxes).C16 n-alkanoic acid was enriched in 13C in periods of high aquatic productivity~750–1650 and 3000–3200 a BP but depleted in 13C in periods of relatively low productivity~150–600 and 2500–3000 a BP.The results indicated that carbon isotope ratios of lipids from phototrophic organisms could be used as new proxies to reconstruct paleo-productivity in Antarctic lakes and ponds and therefore improve our understanding of past climate changes.

Seasonal changes in TC and WSOC and their ^13C isotope ratios in Northeast Asian aerosols： land surface–biosphere–atmosphere interactions

In order to understand the relative importance of anthropogenic and biological sources of carbonaceous aerosols in Northeast Asia,we measured total carbon(TC)and water-soluble organic carbon(WSOC)and their stable carbon isotope ratios(d^(13)C)in total suspended particulates collected from Sapporo,northern Japan(43.07°N,141.36°E)over a 1-year period(during 2 September 2009and 5 October 2010).Temporal variations of TC showed a gradual decrease from mid-autumn to winter followed by a gradual increase to growing season with a peak in early summer.Both d^(13)C_(TC)and d^(13)C_(WSOC)showed very similar temporal trends with a gradual enrichment of^(13)C from mid-autumn to winter followed by a depletion in the^(13)C to early summer and thereafter it remained stable,except for few cases.Based on the results obtained together with the air mass trajectories,we found that biogenic emissions including biological particles(e.g.,pollen)and secondary organic aerosol formation from biogenic volatile organic compounds are the important sources of carbonaceous aerosols in spring/summer whereas fungal spores from soil and biomass burning and enhanced fossil fuel combustion contribute significantly in autumn/winter and in winter,respectively,in Northeast Asia.

Multi-collector ICP-MS Analysis of Pb Isotope Ratios in Rocks: Data, Procedure and Caution

The authors measured Pb isotope compositions of seven USGS rock referencestandards, i.e. AGV-1, AGV-2, BHVO-1, BHVO-2, BCR-2, BIR-1/1 and W-2, together with NBS 981 using amicromass isoprobe multi-collector inductively-coupled plasma mass spectrometer (MC-ICP-MS) at theUniversity of Queensland. ^(203)Tl-^(205)Tl isotopes were used as an internal standard to correctfor mass-dependant isotopic fractionation. The results for both NBS 981 and USGS rock standardsAGV-1 and BHVO-1 are comparable to or better than double- and triple-spike TIMS (thermal ionizationmass spectrometry) data in precision. The data for BHVO-2 and, to a lesser extent, AGV-2 and BCR-2are reproducibly higher for ^(206)Pb/^(204)Pb, ^(207)Pb/^(204)Pb and ^(208)Pb/^(204)Pb thandouble-spike TIMS data in the literature. The authors also obtained the Pb isotope data for BIR- 1/1and W-2, which may be used as reference values in future studies. It is found that linearcorrection for Pb isotopic fractionation is adequate with the results identical to those correctedfollowing an exponential law or a power law. Precise ^(207)Pb/^(206)Pb, ^(208)Pb/^(206)Pb and^(208)Pb/^(207)Pb ratios can be acquired for sample solutions with Pb>=1 ppb. However, Pb isotoperatios involving ^(204)Pb (i.e., ^(206)Pb/^(204)Pb, ^(207)Pb/^(204)Pb and ^(208)Pb/^(204)Pb) arereliable for solutions with Pb>=40 ppb. The errors for Pb isotope ratio analysis using the MC-ICP-MSare dominated by errors in the analysis of ^(204)Pb, which is commonly ascribed to the difficultyand imprecise correction for a ^(204)Hg isobaric interference. It is found however that the majorerrors on ^(204)Pb come from the tailings of mass ^(203)Tl and mass ^(205)Tl These mass tailingslead to over-subtraction of the baseline for ^(204)Pb, which is measured at +-0.5 amu on both sidesof mass-204 (i.e., at amu 203.5 and 204.5 respectively). Such errors are insignificant for Pb-richsample solutions (i.e., high Pb/Tl ratios), but can be severe for low-Pb sample solutions whenover-'spiked' with Tl. Experiments in this study suggest that a minimum concentration ratio ofPb/Tl>5 in Tl-'spiked' solutions be required to ensure reliable ^(206)Pb/^(204)Pb, ^(207)Pb/^(204)Pband ^(208)Pb/^(204)Pb isotopic ratios. The tailings of ^(203)Tl and ^(205)Tl can also lead toover-subtraction of baselines for ^(202)Hg (at amu 202.5) and ^(206)Pb (at amu 205.5). Therefore,the elegance of using ^(203)Tl and ^(205)Tl isotopes for mass fractionation correction becomes asevere problem in low-Pb rock solution-caution is required. Alternative internal standards for massfractionation correction may be considered. Of course, significant instrumental refinement inabundance sensitivity is in demand.

Identification of Pu and U isotopic composition and its applications in environmental and CBRN research

This paper describes the most common presently used methods for detecting uranium and plutonium isotopes after their introduction to environment. Known isotope ratios of U and Pu in different nuclear events are important tool for characterizing the sources of nuclear material. Detection techniques both in field and in laboratory are presented, as well as different models that can be used for identifying the origin and age of the nuclear material. Identification of the source of nuclear material in environmental samples is needed for estimating the quality and quantity of the nuclear hazard. This information is essential in risk assessment and crisis management, in chemical, biological, radiological and nuclear(CBRN) research after e.g. a terrorist attack, in radioecology and environmental radioactivity research.

Oxygen and hydrogen isotope ratios of chert from the Sixtymile Formation in Grand Canyon National Park,USA：a warm palaeoclimate,freshwater deposit

New oxygen and hydrogen isotope ratios of chert from middle, intraformational breccias, and upper breccia members of the Sixtymile Formation（SMF） in eastern Grand Canyon National Park（AZ） yield palaeoclimate estimates between 27 and 33℃. The isotopic compositions of cherts define a domain approximately parallel to the meteoric water line when plotted on a δD–δ-（18）O diagram; these data indicate that meteoric water was involved during formation of the chert. In thin section, the absence of interlocking mega quartz（〉35 lm） and silicafilled fractures and veins, along with preserved micromorphological silica fabrics, suggest that the chert has not been permeated by later hydrothermal fluids. Petrographic observations in thin section such as cyclic silica precipitation phases and glaebular micromorphologic fabrics lend support to the interpretation that meteoric waters were involved during chert precipitation. The post 742 Ma SMF has been correlated with diamictite（transition） beds of the Kingston Peak Formation（CA）, which in turn have been interpreted to have been deposited during the Sturtian Ice Age（-750–700 Ma）. Absence of facetted and striated clasts and other diagnostic glaciogenic features in the SMF,an unconformable contact with the stratigraphically older Chuar Group, coupled with warm palaeotemperature data inferred from stable isotope values of chert, tentatively suggest that deposition of sediment in the SMF likely did not take place during the Sturtian Ice Age.

Elemental and Isotopic Signatures in the Sediments Influenced by Seal Excrement on Antarctic Fildes Peninsula and Their Potential Paleoecological Applications

The elemental and isotopic signatures in the sediments influenced by seal excrement on Antarctic Fildes Peninsula are examined for their potential palaeoecologlcal applications. The seal hair abundance in sediments exhibits remarkable fluctuation versus depth, indicating similar changes in historical populations of the seals visiting the marine terrace. The combination of δ^13 C, total organic carbon concentration （TOC）, total nitrogen concentration （TN） and atomic C/N ratio shows that the organic matters in sediments with numerous seal hairs have a marine origin and are predominantly derived from seal excrements. The large δ15 N values in sediments are attributed to trophic enrichment and NH3 vollatilization processes. The large variations in the δ^15 N values and the negative correlation between the δ15 N values and the seal hair abundances seem to be the results of changes in the paleoclimates and the volatilization rates of the ammonia produced in the seal excrements. The 87 Sr/86 Sr ratios in the acid-soluble fraction of sediments are interpreted as a mixture of the ones from the seal excrements （30%-50%） and the chemically weathered local bedrocks （70%-50%）. The calculated proportion of seal-derived Sr based on the ^87 Sr/^86 Sr ratios has a significant correlation with seal hair abundances in sediments. These results suggest that δ15 N values and the ^87 Sr/^86 Sr ratios in the acid-soluble fraction of sediments were influenced by seal excrements, similar to seal halt numbers, and thus can potentially be used to estimate the historical seal population in the Antarctic region.

Isotopic and Chemical Characteristics of Lagoon Waters in Niigata Prefecture, Japan

In order to investigate the isotopic and chemical characteristics of lagoon waters in Niigata Prefecture in recent years, oxygen and hydrogen stable isotope ratios （i.e., 8180 and 6D）, the concentrations of DOC （dissolved organic carbon）, DO （dissolved oxygen） and pH, etc. in water samples of Sakata and Toyanogata were measured. Samples were generally taken monthly at the fixed sampling points from these lagoons. Consequently, the following matters have been mainly clarified： （1） ~D value of water samples in Sakata was generally larger than that in Toyanogata similarly to the case of ~180, though remarkable large difference among samples was not found; （2） the pH value of lagoon water samples is almost 6.5-8.5 （which is generally larger than that of river water）, and pH at the spot of SI （downstream point of Lower Lagoon （Shitakata）） is remarkably high （9.0-9.5）; （3） Lagoon water has the chemical characteristics contrasting to groundwater with a focus on river water from the viewpoint of pH （acidity or alkalinity） and DO. These matters can be closely related to the biological activity such as photosynthesis due to aquatic plant and phytoplankton and the activity of Crustacea plankton etc. in lagoon.

Oxygen Stable Isotopic Ratio in Precipitations in Niigata Prefecture, Japan

Time-course of oxygen stable isotopic ratios （i.e., δ^18O） as well as seasonal variation of δ^18O has been examined to investigate the characteristics, sources and the passing route of precipitations in Niigata Prefecture. The precipitation samples have been mainly collected with a filtrating bulk sampler at the rooftop of Niigata University. Furthermore, backward trajectories analyses have been also conducted for these samples taken sequentially for a short period. Consequently, the following features have been mainly clarified for the precipitations in Niigata Prefecture： （1） the δ^18O values varied between -14.57%o and -3.86%0 in the precipitations of Niigata University; （2） as for the comparison among sampling points, the mean value of δ^18O at seaside spots （i.e., Niigata City： -6.93%0） is larger than that of inland spots （Sanjyo City： -8.68%0）; （3） δ^18O value was generally small in the rainy or typhoon season, and relatively large in summer; （4） decreasing δ^18O content with time is a predominant feature of sequentially sampled rainfalls as predicted by Rayleigh models of atmospheric vapor condensation.

Late Holocene glacier variations indicated by theδ18O of ice core enclosed gaseous oxygen in the central Tibetan Plateau

Theδ18O of ice core enclosed gaseous oxygen(δ18Obub)has been widely used for climate reconstruction in polar regions.Yet,less is known about its climatic implication in the mountainous glaciers as the lack of continuous record.Here,we present a long-term,continuousδ18Obub record from the Tanggula glacier in the central Tibetan Plateau(TP).Based on comparisons of its variation with regional climate and glacier changes,we found that there was a good correlation between the variation of theδ18Obub in this alpine ice core and the accumulation and melting of this glacier.The more developed the firn layer on glacier surface,the more positive theδ18Obub.Conversely,the more intense the glacier melting,the more negative theδ18Obub.Combined with the chronology of ice core enclosed gases,the glacier variations since the late Holocene in the central TP were reconstructed.The result showed that there were four accumulation and three deficit periods of glaciers in this region.The strongest glacier accumulation period was 1610-300 B.C.,which corresponds to the Neoglaciation.The most significant melting period was the last 100 years,which corresponds to the recent global warming.The Medieval Warm Period was relatively significant in the central TP.However,during the Little Ice Age,there was no significant glacier accumulation in the central TP,and even short deficit events occurred.Comparisons of the late Holocene glacier variation in the central TP with glacier and climate variations in the TP and the Northern Hemisphere showed that it was closely related to the North Atlantic Oscillation.

Differential distribution of authenticity results of different varieties of refined honey based on stable isotope ratio method

Objective Using the stable isotope ratio method for the authenticity identification and variety identification of refined honey.Methods In this paper,a total of 17 samples of different varieties of refined honey were used to obtain refined honey proteins by precipitation with sodium tungstate solution and sulphuric acid solution.The isotope mass spectrometer was used to simultaneously detect theδ^(13)C values of refined honey proteins and refined honey as well as theδ^(18)O andδ^(2)H values of refined honey,processed of the results obtained,analysed the authenticity of the samples and conduct a variety identification study.Results Tested of the resulting honey samples,the results showed that four batches of refined honey did not up to standard,two batches of C-4 vegetable syrup were detected as adulterated,and two batches of protein were not detected.Theδ^(18)O andδ^(2)H values of refined honey were also found to be effective in distinguishing the varietal origin of refined honey to a certain extent.Conclusions The stable isotope ratio method is useful in the authenticity identification of refined honey,and provides new ideas to further promote the authenticity of refined honey and variety identification research.

稳定同位素比技术用于橄榄油的掺假鉴定

市场上橄榄油掺假现象屡禁不止,传统鉴定方法存在局限性。本研究利用元素分析仪-稳定同位素比质谱仪(elemental analyzer-isotope ratio mass spectrometer,EA-IRMS)对市场上常见的7种植物油进行氢、碳稳定同位素比值检验,并对测量结果进行显著性差异分析,同时分析橄榄油中氢、碳稳定同位素比值的相关性。结果表明:橄榄油中δD范围为-146.78‰~-125.30‰,δ^(13)C范围为-29.72‰~-28.59‰,与其他品类植物油中氢稳定同位素比值差异显著(P<0.05),与除葵花籽油、野山茶油外的植物油中碳稳定同位素比值差异显著(P<0.05);且橄榄油中氢、碳稳定同位素比值具有较强的相关性(Pearson’s r=0.904)。计算模拟豆油、玉米油对橄榄油掺假的情况,结果表明,氢、碳稳定同位素比结合分析最低能检测出玉米油掺假10%、豆油掺假30%以上的情况。该研究可为橄榄油的掺假鉴定提供方法参考。

Distribution and quantification of Pb in an evergreen broadleaved forest in three hydrological years

The distribution,quantification and fluxes of Pb were examined in an evergreen broadleaved forest in western Greece for three hydrological years.More specifically,concentrations and annual fluxes of Pb were determined in bulk and throughfall deposition as well as litterfall.The Pb concentrations were also measured in forest floor and mineral soil up to 80 cm and the isotopic ratios of 206Pb/207Pb were determined in soil layers and the parent rock material.High variability in the fluxes of the metal among the three hydrological years were found,evidence of the variability of Pb deposition in time.Litterfall fractions with a large surface area,like holm oak flowers,had high Pb concentrations.Applying a steady state model and considering the Pb amounts in throughfall and litterfall as inputs on the forest floor,the mean residence time of Pb in the forest floor was 94 years with a coefficient of variation equal to 41%.More observations are needed to lower the variability of the mean residence time.The isotopic ratio in the rock material was defined as the lithogenic ratio.The statistical tests showed that the petrol derived Pb migrated to the depth of 20 cm and its percentages in the soil pedon was in the range of 62%in the L horizon to 11%in the 10–20cm layer.In higher depths(>40 cm)preindustrial anthropogenic Pb affected the isotopic ratio.As the forest under consideration is remote from industrial activities,the results can serve as a baseline for future studies on Pb distribution and quantification.

Crustal Composition of China Continent Constrained from Heat Flow Data and Helium Isotope Ratio of Underground Fluid

Based on conservation of energy principle and heat flow data in China continent, the upper limit of 1.3 μW/m3 heat production is obtained for continental crust in China. Furthermore, using the data of heat flow and helium isotope ratio of underground fluid, the heat productions of different tectonic units in China continent are estimated in range of 0.58-1.12 μW/m3 with a median of 0.85 μW/m3. Accordingly, the contents of U, Th and K20 in China crust are in ranges of 0.83-1.76 μg/g, 3.16-6.69 μg/g, and 1.0%-2.12%, respectively. These results indicate that the abundance of radioactive elements in the crust of China continent is much higher than that of Archean crust; and this fact implies China＇s continental crust is much evolved in chemical composition. Meanwhile, significant lateral variation of crustal composition is also exhibited among different tectonic units in China continent. The crust of eastern China is much enriched in incompatible elements such as U, Th and K than that of western China; and the crust of orogenic belts is more enriched than that of platform regions. It can also be inferred that the crusts of eastern China and orogenic belts are much felsic than those of western China and platform regions, respectively, derived from the positive correlation between the heat production and SiO2 content of bulk crust. This deduction is consistent with the results derived from the crustal seismic velocity data in China. According to the facts of the lower seismic velocity of China than the average value of global crust, and the higher heat production of China continent compared with global crust composition models published by previous studies, it is deduced that the average composition models of global continent crust by Rudnick and Fountain （1995）, Rudnick and Gao （2003）, Weaver and Tarney （1984）, Shaw et al. （1986）, and Wedepohl （1995） overestimate the abundance of incompatible elements such as U, Th and K of continental crust.

Clay minerals and geochemistry of the bottom sediments in the northwestern East China Sea

Clay minerals of 34 sediments collected from the northwestern continental shelf of the East China Sea have been determined by X-ray diffraction analysis. The clay mineral distribution is mainly controlled by the sediment source and the dominant circulation pattern. The predominant clay mineral in our study area is illite comprising more than 67% of the whole clay fraction. The highest concentration of illite （〉68%） is found in the southeastern offshore parts beyond the reach of terrigenous input from the Jeju Island. It means that these illites are largely transported by the Kuroshio Current from the South China Sea （SCS）. Smectite is highly concentrated in the northwest middle part and in the outer-shelf mud patch. It seems to be due to the high supply of smectite transported from China where fine-grained sediments are discharged from modern and ancient Huanghe （Yellow） River. The relatively high abundant kaolinite is likely derived from the Changjiang （Yangtze） River via the Taiwan Warm Current. In contrast, large amounts of chlorite and high chlorite/kaolinite ratios occur in the northwestern area, reflecting the transportation by the Yellow Sea Coastal Current from the southern Yellow Sea. The discrimination diagrams clearly show that the sediments in the northwestern East China Sea are ultimately sourced from Chinese rivers, especially from the Huanghe River, whereas the sediment in the northeast part might come from the Jeju Island. The muddy sediments of the Changjiang River＇s submerged delta have much lower 87Sr/S6Sr ratios （0.716 2-0.718 0） than those of the Shandong Peninsular mud wedge （0.721 6-0.724 9）, which are supposed to be originated from the Huanghe River, suggesting the distribution pattern of 87Sr/86Sr ratios as a new tracer to discriminate the provenance of shelf sediments in the study area. The 87Sr/86Sr ratios of the outer-shelf muddy sediments ranged from 0.7169 to 0.7216 in a wide range and was between those of the Huanghe River and Changjiang River sediments, suggesting multiple sources of the sediment in the area.

An online method to determine chlorine stable isotope composition by continuous flow isotope ratio mass spectrometry (CF-IRMS) coupled with a Gasbench Ⅱ

An online method using continuous flow isotope ratio mass spectrometry （CF-IRMS） interfaced with a Gasbench Ⅱ was presented to determine chlorine stable isotope composition. Silver chloride （AgCl） was quantitatively derived from chloride by using silver nitrate （AgNO3）, and then was reacted with iodomethane （CH3Ⅰ） to produce methyl chloride （CH3Cl）. A GasBench Ⅱ equipped with a PoraPlot Q column was used to separate CH3Cl from any other gas species. Finally, chlorine stable isotope analysis was carried out on CH3Cl introduced to the IRMS in a helium stream via an active open split. The minimum amount of Cl used in this method is of the order of 1.4 μmol. Inter-laboratory and inter-technique comparisons show that the total uncertainty incorporating both the precision and accuracy of this method is better than 0.007%. Furthermore, ten seawaters sampled from different locations have a narrow δ37Cl value range from -0.008% to 0.010%, with a mean value of （0.000±0.006）%. This supports the assumption that any seawater can be representative of standard mean ocean chloride （SMOC） and used as an international reference material.

A Pilot Study of Trophic Level and Human Origins at the Xiaoshuangqiao Site, China(ca. 1400 BC) Using 8D Values of Collagen

We present here a pilot study to examine trophic level effects and migration patterns at the middle Shang Dynasty site of Xiaoshuangqiao in Henan Province using δD results combined with δ^13C and δ^15N values. A total of 33 specimens（17 humans, 7 cattle, 5 pigs, 3 sheep, 1 dog） of bone collagen were isotopically analyzed for δ^13C, δ^15N, and dD values. A strong positive correlation（R^2 = 0.94）between mean δ^15N and δD values of herbivores（cattle and sheep）, omnivores（pig）, carnivores（dog）and humans was observed. The δD results were found to increase by -10‰ to 20‰ from herbivores to omnivores to carnivorous, evidence that collagen δD results are a useful indicator for the study of trophic levels and dietary patterns at archaeological sites. The δD results were also used to examine the origins of two different groups of individuals buried at Xiaoshuangqiao. Individuals buried in sacrificial pits of district V had mean δD values（-47.0 ± 2.9‰, n = 11） that were significantly（p =0.049） elevated compared to the people buried in the stratigraphy of district IX（-51.3 ± 3.3‰, n = 3）,indicating that they were ingesting water from different locations. In addition, the D values of the people buried in the stratigraphy were similar to the pigs（-54.5 ± 4.2‰, n = 5） at Xiaoshuangqiao,suggesting that they were most probably of the local population, and that the individuals buried in the sacrificial pits were most possibly from the coast and prisoners of the Dongyi（“东夷”）people. Thus,δD results have the potential to examine human origins and migration patterns and should be increasingly used in conjunction with δ^13C and δ^15N values at archaeological sites.

Tree-ring δ^(15)N of Qinghai spruce in the central Qilian Mountains of China:Is pre-treatment of wood samples necessary?

A knowledge of the tree-ring stable nitrogen isotope ratio(δ^(15)N)can deepen our understanding of forest ecosystem dynamics by indicating the long-term availability,cycling and sources of nitrogen(N).However,the radial mobility of N blurs the interannual variations in the long-term N records.Previous studies of the chemical extraction of tree rings before analysis had produced inconsistent results and it is still unclear whether it is necessary to pre-treat wood samples from specific tree species to remove soluble N compounds before determining theδ^(15)N values.We compared the effects of pre-treatment with organic solvents and hot ultrapure water on the N concentration andδ^(15)N of tree rings from endemic Qinghai spruce(Picea crassifolia)growing in the interior of the central Qilian Mountains,China,during the last 60 a.We assessed the effects of different preparation protocols on the removal of the labile N compounds and investigated the need to pre-treat wood samples before determining theδ^(15)N values of tree rings.Increasing trends of the tree-ring N concentration were consistently observed in both the extracted and unextracted wood samples.The total N removed by extraction with organic solvents was about 17.60%,with a significantly higher amount in the sapwood section(P<0.01).Theδ^(15)N values of tree rings decreased consistently from 1960 to 2019 in both the extracted and unextracted wood samples.Extraction with organic solvents increased theδ^(15)N values markedly by about 5.2‰and reduced the variations in theδ^(15)N series.However,extraction with hot ultrapure water had little effect,with only a slight decrease in theδ^(15)N values of about 0.5‰.Our results showed that the radial pattern in the inter-ring movement of N in Qinghai spruce was not minimized by extraction with either organic solvents or hot ultrapure water.It is unnecessary to conduct hot ultrapure water extraction for the wood samples from Qinghai spruce because of its negligible effect on the removal of the labile N.Theδ^(15)N variation trend of tree rings in the unextracted wood samples was not influenced by the heartwood-sapwood transition zone.We suggest that theδ^(15)N values of the unextracted wood samples of the climate-sensitive Qinghai spruce could be used to explore the ecophysiological dynamics while focusing on the long-term variations.

Kinetic Modeling the Formation of Low-mature Gases and Analysis of the Possibility to Be Accumulated

At present, shallow gases have received much attention due to low cost in exploration and production. Low-mature gases, as one significant origin to shallow gas, turns to be an important research topic. The present understanding of low-mature gases is confined within some geological cases, and few laboratory studies have been reported. Therefore, the potential and characters of low- mature gases are not clear up to now. Here, two premature samples （one coal and the other shale） were pyrolyzed in a gold confined system. The gaseous components including hydrocarbon gases and non-hydrocarbon gases were analyzed. Based on kinetic modeling, the formation of low-mature gases was modeled. The results showed that during low mature stage, about 178 mL/gTOC gas was generated from the shale and 100 mL/gTOC from the coal. Two third to three fourth of the generated gases are non-hydrocarbon gases such as H2S and CO2. The total yields of C1-5 for the two samples are almost the same, 30-40 mL/gTOC, but individual gaseous hydrocarbon is different. The shale has much lower C1 but higher C2-5, whereas the coal has higher C1 but lower C2-5. Hydrocarbon gases formed during low-mature stage are very wet. The stable carbon isotope ratios of methane range from -40‰ to -50‰ （PDB）, in good consistence with empiric criterion for low-mature gases summed up by the previous researchers. The generation characters suggest that the low-mature gases could be accumulated to form an economic gas reservoir, but most of them occur only as associated gases.

Altitudinal trends in δ^13C value,stomatal density and nitrogen content of Pinus tabuliformis needles on the southern slope of the middle Qinling Mountains,China

In this study,a coniferous tree species(Pinus tabuliformis Carr.) was investigated at a moderate-altitude mountainous terrain on the southern slope of the middle Qinling Mountains(QLM) to detect the trends in carbon isotope ratio( δ^(13)C),leaf nitrogen content(LNC) and stomatal density(SD) with altitude variation in northsubtropical humid mountain climate zone of China.The results showed that LNC and SD both significantly increased linearly along the altitudinal gradient ranging from 1000 to 2200 m,whereas leafδ^(13)C exhibited a significantly negative correlation with the altitude.Such a correlation pattern differs obviously from that obtained in offshore low-altitude humid environment or inland high-altitude semi-arid environment,suggesting that the pattern of increasing δ^(13)C with the altitude cannot be generalized.The negative correlation between δ ^(13)C and altitude might be attributed mainly to the strengthening of carbon isotope fractionation in plants caused by increasing precipitation with altitude.Furthermore,there was a remarkable negative correlation between leaf δ ^(13)C and LNC.One possible reason was that increasing precipitation that operates to increase isotopic discrimination with altitude overtook the LNC in determining the sign of leaf δ ^(13)C.The significant negative correlation between leaf δ ^(13)C and SD over altitudes was also found in the present study,indicating that increases in SD with altitude would reduce,rather than enhance plant δ^(13)C values.