以[^(14)C]碳酸钡为放射性同位素原料,通过格氏反应、Curtius重排、亲核加成、硫代及关环等7步反应,制备了同位素碳-14标记的毒氟磷粗品,经反相高效液相色谱(RP-HPLC)纯化获得标记物纯品^(14)C-毒氟磷(N-[2-(4-甲基苯并[2-^(14)C]噻唑基...以[^(14)C]碳酸钡为放射性同位素原料,通过格氏反应、Curtius重排、亲核加成、硫代及关环等7步反应,制备了同位素碳-14标记的毒氟磷粗品,经反相高效液相色谱(RP-HPLC)纯化获得标记物纯品^(14)C-毒氟磷(N-[2-(4-甲基苯并[2-^(14)C]噻唑基)]-2-氨基-2-氟代苯基-O,O-二乙基甲基膦酸酯,38.3 m Ci)。7步反应的化学收率/放化收率为10%。其结构经核磁共振氢谱、质谱和放射性高效液相色谱(HPLC-FSA)分析确认。放射性薄层成像分析(TLC-IIA)、高效液相色谱-液体闪烁测量联用分析(HPLC-LSC)、高效液相色谱-流动液体闪烁测量/二极管阵列检测器/质谱联用分析(HPLC-FSA/PDA/MS)和LSC分析表明,^(14)C-毒氟磷的放化纯度和化学纯度均大于98%,比活度为58.0 m Ci/mmol,可作为放射性示踪剂,用于毒氟磷的代谢和环境行为等研究。展开更多
以[^(14)C]碳酸钡为放射性同位素原料,通过乙炔环三聚、苯羧基化和甲基化、胺化、环化、亲核取代、格氏、还原、氧化等反应和反相高效液相色谱(HPLC)纯化获得了2种放射性同位素碳-14标记毒氟磷[N-[2-(4-甲基[苯基-U-^(14)C_6]苯并噻唑基...以[^(14)C]碳酸钡为放射性同位素原料,通过乙炔环三聚、苯羧基化和甲基化、胺化、环化、亲核取代、格氏、还原、氧化等反应和反相高效液相色谱(HPLC)纯化获得了2种放射性同位素碳-14标记毒氟磷[N-[2-(4-甲基[苯基-U-^(14)C_6]苯并噻唑基)]-2-氨基-2-氟苯基-O,O-二乙基甲基膦酸酯(2,20.6 m Ci)和N-[2-(4-甲基苯并噻唑基)]-2-氨基-2-氟苯基-O,O-二乙基[^(14)C]甲基膦酸酯(3,32.4 m Ci)],其结构经核磁共振氢谱(~1H NMR)和在线放射性高效液相色谱-二极管阵列检测器/质谱联用(HPLC-FSA/PDA/MS)分析确认,反应总放化收率/化学收率分别为31%和67%.放射性薄层层析-同位素成像分析(TLC-IIA)、离线放射性高效液相色谱(HPLC-LSC),HPLC-FSA/PDA/MS和液体闪烁测量(LSC)分析表明,两种标记物的放化纯度和化学纯度均大于98%,比活度分别为25.5,55.5 m Ci/mmol.该标记物可作为放射性示踪剂,用于毒氟磷的代谢、残留和环境行为等研究.展开更多
Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope(their δ18O values range from-0.3‰--0.1‰) and lighter oxygen isotope(their δ18O val...Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope(their δ18O values range from-0.3‰--0.1‰) and lighter oxygen isotope(their δ18O values range from-22.1‰--19.5‰).Generally,they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water.This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones,preserving intragranular volume and providing the mass basis for later disso-lution caused by acidic fluid flow to produce secondary porosity.Ferriferous calcites are characterized by relatively light carbon isotope with δ13C values ranging from-8.02‰ to-3.23‰,and lighter oxygen isotope with δ18O values ranging from-22.9‰ to-19.7‰,which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis.As the mid-late diagenetic products,ferriferous calcites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir.The late ankerite is relatively heavy in carbon isotope with δ13C values ranging from-1.92‰ to-0.84‰,and shows a wide range of variations in oxygen isotopic composition,with δ18O values ranging from-20.5‰ to-12.6‰.They are believed to have nothing to do with decarboxylation,but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation,and the alkaline diagenetic environment at the mid-late stage would promote this process.展开更多
In recent years big strides have been made in the exploration of ores in the central-south segment of the Da Hinggan Ling Range,though some debates still exist on the metallogenesis and sources of ore-forming material...In recent years big strides have been made in the exploration of ores in the central-south segment of the Da Hinggan Ling Range,though some debates still exist on the metallogenesis and sources of ore-forming materials.Pyrite and other sulfides in direct relation to the Pb-Zn-Ag ore deposits were chosen for the He and Ar isotopic analysis of ore-forming fluids,and the first He and Ar isotope data have been obtained from the study region.3He/4He ratios in 14 samples collected from 7 mining districts are 2.17×10-6-12.52×10-6,averaging 6.86×10-6 and their R/Ra ratios are 1.56-9.01 Ra,averaging 4.37 Ra.By projecting the data points onto the 3He-4He concentrations diagram,all the points fall near the mantle helium area.The calculated mantle-source helium ratios are within the range of 19.58%-76.96%,with an average of 49.52%.Argon isotopic characteristics are close to those of mantle source,indicating that the ore-forming material was transport upwards via the multi-stage evolution of mantle plume and concentrated as ores in the favorable loci of mantle branch structures.展开更多
Hydrogen isotopes of n-alkanes in grasses, tree leaves and reeds from six regions with latitudes of 20° to 39°N in China are measured by GC-TC-IRMS analytical technique in order to understand their hy- droge...Hydrogen isotopes of n-alkanes in grasses, tree leaves and reeds from six regions with latitudes of 20° to 39°N in China are measured by GC-TC-IRMS analytical technique in order to understand their hy- drogen isotopic compositions and environmental significance. The results show that a difference in δ D values (from -42.1‰ to -66.6‰) of n-alkanes exists among the same kinds of plants from various re- gions. Hydrogen isotopic compositions of most even carbon numbered n-alkanes in every plant are slightly heavier than that of the odd homologues. A trend toward D-enrichment with increasing chain length of n-alkanes in most plant samples is observed. Mean δ D values of n-alkanes in the studied plants range from -202.6‰ to -130.7‰ and the reed from a salt marsh has the largest value. The mean δ D values of individual n-alkanes among the same kinds of plants from various regions have the characteristics of leaf > reed > grass. The hydrogen isotopic compositions of n-alkanes are apparently distinct among various kinds of plants from the same region and the mean δ D values exhibit a distri- bution of tree leaf > reed > grass. It is observed that the mean δ D values of n-alkanes and δ D values of C27 and C29 n-alkanes in the grasses and tree leaves from these studied regions correlate clearly nega- tively with latitude and positively with temperature, indicating that these values can be used as excel- lent indicators of environment and climate. These results provide important basic data for under- standing the distributional law of hydrogen isotopes of individual n-alkanes and their applied research.展开更多
文摘以[^(14)C]碳酸钡为放射性同位素原料,通过格氏反应、Curtius重排、亲核加成、硫代及关环等7步反应,制备了同位素碳-14标记的毒氟磷粗品,经反相高效液相色谱(RP-HPLC)纯化获得标记物纯品^(14)C-毒氟磷(N-[2-(4-甲基苯并[2-^(14)C]噻唑基)]-2-氨基-2-氟代苯基-O,O-二乙基甲基膦酸酯,38.3 m Ci)。7步反应的化学收率/放化收率为10%。其结构经核磁共振氢谱、质谱和放射性高效液相色谱(HPLC-FSA)分析确认。放射性薄层成像分析(TLC-IIA)、高效液相色谱-液体闪烁测量联用分析(HPLC-LSC)、高效液相色谱-流动液体闪烁测量/二极管阵列检测器/质谱联用分析(HPLC-FSA/PDA/MS)和LSC分析表明,^(14)C-毒氟磷的放化纯度和化学纯度均大于98%,比活度为58.0 m Ci/mmol,可作为放射性示踪剂,用于毒氟磷的代谢和环境行为等研究。
文摘以[^(14)C]碳酸钡为放射性同位素原料,通过乙炔环三聚、苯羧基化和甲基化、胺化、环化、亲核取代、格氏、还原、氧化等反应和反相高效液相色谱(HPLC)纯化获得了2种放射性同位素碳-14标记毒氟磷[N-[2-(4-甲基[苯基-U-^(14)C_6]苯并噻唑基)]-2-氨基-2-氟苯基-O,O-二乙基甲基膦酸酯(2,20.6 m Ci)和N-[2-(4-甲基苯并噻唑基)]-2-氨基-2-氟苯基-O,O-二乙基[^(14)C]甲基膦酸酯(3,32.4 m Ci)],其结构经核磁共振氢谱(~1H NMR)和在线放射性高效液相色谱-二极管阵列检测器/质谱联用(HPLC-FSA/PDA/MS)分析确认,反应总放化收率/化学收率分别为31%和67%.放射性薄层层析-同位素成像分析(TLC-IIA)、离线放射性高效液相色谱(HPLC-LSC),HPLC-FSA/PDA/MS和液体闪烁测量(LSC)分析表明,两种标记物的放化纯度和化学纯度均大于98%,比活度分别为25.5,55.5 m Ci/mmol.该标记物可作为放射性示踪剂,用于毒氟磷的代谢、残留和环境行为等研究.
文摘Early carbonate cements in the Yanchang Formation sandstones are composed mainly of calcite with relatively heavier carbon isotope(their δ18O values range from-0.3‰--0.1‰) and lighter oxygen isotope(their δ18O values range from-22.1‰--19.5‰).Generally,they are closely related to the direct precipitation of oversaturated calcium carbonate from alkaline lake water.This kind of cementation plays an important role in enhancing the anti-compaction ability of sandstones,preserving intragranular volume and providing the mass basis for later disso-lution caused by acidic fluid flow to produce secondary porosity.Ferriferous calcites are characterized by relatively light carbon isotope with δ13C values ranging from-8.02‰ to-3.23‰,and lighter oxygen isotope with δ18O values ranging from-22.9‰ to-19.7‰,which is obviously related to the decarboxylation of organic matter during the late period of early diagenesis to the early period of late diagenesis.As the mid-late diagenetic products,ferriferous calcites in the study area are considered as the characteristic authigenic minerals for indicating large-scaled hydrocarbon influx and migration within the clastic reservoir.The late ankerite is relatively heavy in carbon isotope with δ13C values ranging from-1.92‰ to-0.84‰,and shows a wide range of variations in oxygen isotopic composition,with δ18O values ranging from-20.5‰ to-12.6‰.They are believed to have nothing to do with decarboxylation,but the previously formed marine carbonate rock fragments may serve as the chief carbon source for their precipitation,and the alkaline diagenetic environment at the mid-late stage would promote this process.
文摘In recent years big strides have been made in the exploration of ores in the central-south segment of the Da Hinggan Ling Range,though some debates still exist on the metallogenesis and sources of ore-forming materials.Pyrite and other sulfides in direct relation to the Pb-Zn-Ag ore deposits were chosen for the He and Ar isotopic analysis of ore-forming fluids,and the first He and Ar isotope data have been obtained from the study region.3He/4He ratios in 14 samples collected from 7 mining districts are 2.17×10-6-12.52×10-6,averaging 6.86×10-6 and their R/Ra ratios are 1.56-9.01 Ra,averaging 4.37 Ra.By projecting the data points onto the 3He-4He concentrations diagram,all the points fall near the mantle helium area.The calculated mantle-source helium ratios are within the range of 19.58%-76.96%,with an average of 49.52%.Argon isotopic characteristics are close to those of mantle source,indicating that the ore-forming material was transport upwards via the multi-stage evolution of mantle plume and concentrated as ores in the favorable loci of mantle branch structures.
基金Supported by National Natural Science Foundation of China (Grant Nos. 40642007 and 40772069)National Basic Research Program of China (Grant No. 2005CB422105)Special Project for Winners of CAS President Award
文摘Hydrogen isotopes of n-alkanes in grasses, tree leaves and reeds from six regions with latitudes of 20° to 39°N in China are measured by GC-TC-IRMS analytical technique in order to understand their hy- drogen isotopic compositions and environmental significance. The results show that a difference in δ D values (from -42.1‰ to -66.6‰) of n-alkanes exists among the same kinds of plants from various re- gions. Hydrogen isotopic compositions of most even carbon numbered n-alkanes in every plant are slightly heavier than that of the odd homologues. A trend toward D-enrichment with increasing chain length of n-alkanes in most plant samples is observed. Mean δ D values of n-alkanes in the studied plants range from -202.6‰ to -130.7‰ and the reed from a salt marsh has the largest value. The mean δ D values of individual n-alkanes among the same kinds of plants from various regions have the characteristics of leaf > reed > grass. The hydrogen isotopic compositions of n-alkanes are apparently distinct among various kinds of plants from the same region and the mean δ D values exhibit a distri- bution of tree leaf > reed > grass. It is observed that the mean δ D values of n-alkanes and δ D values of C27 and C29 n-alkanes in the grasses and tree leaves from these studied regions correlate clearly nega- tively with latitude and positively with temperature, indicating that these values can be used as excel- lent indicators of environment and climate. These results provide important basic data for under- standing the distributional law of hydrogen isotopes of individual n-alkanes and their applied research.
