Sources and transport of dissolved and particulate organic carbon in the Mississippi River estuary and adjacent coastal waters of the northern Gulf of Mexico

Dissolved organic carbon (DOC), stable carbon isotopic (delta(13)C) compositions of DOC and particulate organic carbon (POC), and elemental C/N ratios of POC were measured for samples collected from the lower Mississippi and Atchafalaya rivers and adjacent coastal waters in the northern Gulf of Mexico during the low flow season in June 2000 and high flow season in April 2001. These isotopic and C/N results combined with DOC measurements were used to assess the sources and transport of terrestrial organic matter from the Mississippi and Atchafalaya rivers to the coastal region in the northern Gulf of Mexico. delta(13)C values of both POC (-23.8parts per thousand to -26.8parts per thousand) and DOC (-25.0parts per thousand to -29.0parts per thousand) carried by the two rivers were more depleted than the values measured for the samples collected in the offshore waters. Strong seasonal variations in delta(13)C distributions were observed for both POC and DOC in the surface waters of the region. Fresh water discharge and horizontal mixing played important roles in the distribution and transport of terrestrial POC and DOC offshore. Our results indicate that both POC and DOC exhibited non-conservative behavior during the mixing especially in the mid-salinity range. Based on a simple two end-member mixing model, the comparison of the measured DOC-delta(13)C with the calculated conservative isotopic mixing curve indicated that there was a significant in situ production of marine-derived DOC in the mid- to high-salinity waters consistent with our in situ chlorophyll-a measurements. Our DOC-delta(13)C data suggest that a removal of terrestrial DOC mainly occurred in the high-salinity (>25) waters during the mixing. Our study indicates that the mid- to high- (10-30) salinity range was the most dynamic zone for organic carbon transport and cycling in the Mississippi River estuary. Variability in isotopic and elemental compositions along with variability in DOC and POC concentrations suggest that autochthonous production, bacterial utilization, and photo-oxidation could all play important roles in regulating and removing terrestrial DOC in the northern Gulf of Mexico and further study of these individual processes is warranted. (C) 2004 Elsevier B.V. All rights reserved.

Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four US estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (delta(13)C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble "uncharacterized" organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, delta(13) C and stable nitrogen (delta(15)N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples. a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of delta(13)C and delta(15)N measured for bulk HMW-DOM varied from -22.1 to -30.1parts per thousand and 2.8 to 8.9parts per thousand, respectively and varied among the four estuaries studied as well. Among the Compound classes, TCHO was more enriched in C-13 (delta(13)C = -18.5 to -22.8parts per thousand) compared with THAA (delta(13)C = -20.0 to -29.6parts per thousand) and total lipid (delta(13)C = -25.7 to -30.7parts per thousand). The acid-insoluble organic fractions, in general, had depleted C-13 values (delta(13)C = -23.0 to -34.4parts per thousand). Our results indicate that the observed differences in both delta(13)C and delta(15)N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures. Copyright (C) 2004 Elsevier Ltd.

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (delta(13)C) compositions and n-alkane (nC(16-38)) concentrations were measured for Spartina alterniflora, a C-4 marsh grass, Typha latifolia, a C-3 marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. delta(13)C values of organic matter preserved in the upper fresh water site sediment were more negative (-23.0+/-0.3) as affected by the C-3 plants than the values of organic matter preserved in the sediments of middle (-18.9+/-0.8) and mud flat sites (-19.4+/-0.1) as influenced mainly by the C4 marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC(21) to nC(33) long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC(29) was the most abundant homologue in all samples measured. Both delta(13)C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters. (C) 2003 Elsevier Ltd. All rights reserved.

高寒草甸生态系统食物链结构分析--来自稳定性碳同位素的证据

稳定性同位素技术应用于生态系统物质流动和食物链营养关系的研究方法,是基于生物体内天然存在的同位素比值与它们食物密切相关这一原理建立起来的.即将生物体内的稳定性同位素比值(如δ~(13)C)作为一自然标记,根据物种间该值的相对差异,追踪生态系统中的主要物质(如碳源)的来源和物质流动.于2002年4～8月测定了高寒草甸生态系统主要生物群落中物种的稳定性碳同位素比值(δ~(13)C),依据得到的系统的富集因子(1.05±0.45)‰,分析并确定了所测物种间的取食与被取食关系.结果发现:高寒草甸生态系统由5条主要的食物链构成,其中1条为"植物→小型哺乳类→食肉兽/猛禽"的三节点食物链,2条为"植物→牲畜和植物→植食性鸟类"的二节点食物链,2条分别为"植物→昆虫→雀形目鸟类→猛禽/食肉兽" 和"植物→昆虫→两栖类→猛禽/食肉兽"的四节点食物链;系统食物链的最大长度为3.53,与系统的最大节点数相近.表明稳定性碳同位素可以作为分析高寒草甸生态系统食物网和食物链结构以及食物链长度的有效代理(proxy).

Diet shift of upland buzzards (Buteo hemilasius): evidence from stable carbon isotope ratios

We measured the stable carbon isotope ratios for muscle of the upland buzzards (Buteo hemilasius), plateau pika (Ochotoma curzoniae), root vole (Microtus oeconomus), plateau zokor (Myospalax fontanierii) and passerine bird species at the Haibei Alpine Meadow Ecosystem Research Station (HAMERS), and provided diet information of upland buzzards with the measurement of stable carbon isotopes in tissues of these consumers. The results showed that δ~(13)C values of small mammals and passerine bird species ranged from -25.57‰ to -25.78‰ (n = 12), and from -24.81‰ to -22.51% (n = 43), respectively, δ~(13)C values of the upland buzzards ranged from -22.60‰ to -23.10‰ when food was not available. The difference in δ~(13)C values (2.88‰±0.31‰) between upland buzzards and small mammals was much larger than the differences reported previously, 1‰-2‰, and showed significant difference, while 1.31‰±0.34‰ between upland buzzard and passerine bird species did not differ from the previously reported trophic fractionation difference of 1‰-2‰. Estimation of trophic position indicated that upland buzzards stand at trophic position 4.23, far from that of small mammals, i.e., upland buzzards scarcely captured small mammals as food at the duration of food shortage. According to isotope mass balance model, small mammals contributed 7.89% to 35.04% of carbon to the food source of the upland buzzards, while passerine bird species contributed 64.96% to 92.11%. Upland buzzards turned to passerine bird species as food during times of shortage of small mammals. δ~(13)C value, a useful indicator of diet, indicates that the upland buzzards feed mainly on passerine bird species rather than small mammals due to "you are what you eat" when small mammal preys are becoming scarce.

A stable carbon isotopic approach for understanding the CO2 flux at the Haibei Alpine Meadow Ecosystem - A simple model

Although respiration of organisms and biomass as well as fossil fuel burning industrial production are identified as the major sources, the CO2 flux is still unclear due to the lack of proper measurements. A mass-balance approach that exploits differences in the carbon isotopic signature (delta(13)C) of CO2 Sources and sinks was introduced and may provide a means of reducing uncertainties in the atmospheric budget. delta(13)C measurements of atmospheric CO2 yielded an average of - 10.3 parts per thousand relative to the Peedee Belemnite standard; soil and plants had a narrow range from -25.09 parts per thousand to -26.51 parts per thousand and averaged at -25.80 parts per thousand. Based on the fact of steady fractionation and enrichment during respiration of mitochondria, we obtained the emission Of CO2 of 35.451 mol m(-2) a(-1) and CO2 flux of 0.2149 mu mol m(-2) s(-)1. The positive CO2 flux indicated the Haibei Alpine Meadow Ecosystem a source rather than a sink. The mass-balance model can be applied for other ecosystem even global carbon cycles because it neglects the complicated process of carbon metabolism, however just focuses on stable carbon isotopic compositions in any of compartments of carbon sources and sinks. (C) 2005 Elsevier B.V. All rights reserved.

Characterization of photosynthetic pathway of plant species growing in the eastern Tibetan plateau using stable carbon isotope composition

The photosynthetic pathway of plant species collected at Menyuan, Henan, and Maduo sites, east of Tibetan Plateau, China, during the growing season were studied using stable carbon isotopes in leaves. The 232 samples leaves analyzed belonged to 161 species, 30 families, and 94 genera. The delta(13)C values (from -24.6 to -29.2 %o) indicated that all the considered species had a photosynthetic C-3 pathway. The absence of plant species with C-4 photosynthetic pathway might be due to the extremely low air temperature characterizing the Tibetan Plateau. The average delta(13)C value was significantly (p < 0.05) different between annuals and perennials at the three considered study sites. Hence the longer-lived species had greater water-use efficiency (WUE) than shorter-lived species, that is, longer-lived species are better adapted to the extreme environmental conditions of the Tibetan Plateau.

黄土中主要温室气体组分特征

Scientists have paid much attention to the greenhouse effects and the greenhouse gases for the fact of global warming. There are many uncertainties in the prediction of future climatic change. One of the important reasons causing the uncertainties is insufficient researches of the sources and sinks of greenhouse gases, especially, there is a missing sink in the global carbon cycle. The recent researches proposal that there may be an important carbon sink in the middle-latitude terrestrial ecosystems (vegetation and soil) in the North Hemisphere, despite that there is much disputation about its position and amplitude. Chinese loess is located in the middle latitude area in the North Hemisphere, what kind of role does it play in and how does it influence on the balance of the global greenhouse gases budget? For this reason, many samples were taken and analyzed from wide range and multi-stratum of Chinese loess to understand characteristics of major greenhouse gases in loess and loess possible effect on global greenhouse gas budget. Using self-made spiral corer, we totally took 81 gas samples and 65 soil samples from 7 loess profiles in China such as Zhaitang loess section of Beijing, Pianguan, Xingxian, Lishi, Puxian, Jishan loess section of Shanxi Province, and Luochuan loess section of Shaanxi Province. The gas concentrations for CO_2, CH_4 and N_2O, the contents of N_2, O_2 and carbonate, and the carbon isotopic compositions of CO_2 and carbonate in loess strata sequences are observed and measured. In addition, 19 gas samples data of the Weinan loess section, Shaanxi Province are combination with this research to study characteristics of greenhouse gases in loess. This research indicates that (1) the free gases in loess are neither paleo-atmospheric gases nor modern atmospheric gases; (2) the concentrations of CO_2, CH_4 and N_2O in loess are higher than atmospheric level; (3) the δ~(13)C of loess CO_2 shows that the CO_2 in loess mainly comes from the oxygenolysis of organic matters, but because of isotopic exchange with carbonate in loess, the carbon isotopic exchange with carbonate in loess, the carbon isotopic compositions of loess CO_2 are much more heavier than organic original CO_2; (4) the concentration of CH_4 in Malan loess is lower because it is not favorable for the decomposition of anaerobic bacteria in the Malan Loess; (5) estimation of the total amount of the carbonate in loess reveals that loess is a huge carbon reservoir (about 850PgC). In addition, the impact of the deuterogenic carbonatization during the loess accumulation on the global carbon cycle was discussed, and the preliminary conclusion is that the research work is still not enough to evaluate the effect of loess on the sources and sinks of the anthropogenic CO_2.

流体地球化学：成因、流动和流体-岩石相互作用及塔里木盆地实例研究

Geofluid in sedimentary basins is related to petroleum generation, migration, accumulation and preservation, and is a topic of geological frontier. By integrating the multi-discipline methods of petroleum geochemistry, sedimentology, hydrogeology, petroleum geology and experimental geochemistry, the thesis has carried out experiments of microcline dissolution in solutions with organic acids, crude oil, brines with high total dissolved solids (TDS), and has dealt with Al distribution between the crude oil and the brines after the experiments. Cases for study includes Central Tarim, Hetianhe Gas Field and Kucha forland basin with data containing fluid chemistry and isotopic compositions, thin sections of sandstones and carbonates, homogenization temperatures and salinities of fluid inclusions, isotopic compositions of bulk rock and autigenic minerals. The aims are to elucidate fluid origin and flow in the three areas, effect of hydrocarbon emplacement on diagenesis, and to show occurrence of microbe-mediated, and thermochemical sulfate reduction in the Tarim Basin. Microcline dissolution experiments show that after 100 hour, part of the dissolved Al distributes in the crude oil, and the Al concentrations in the crude oil rise when organic acids are added. The result can be used to explain that most oilfield waters in the Tarim Basin are characterized by less than 3mg/L Al. Crude oil added to the solutions can enhance microcline dissolution, which is also observed in the case - Silurian sandstones with early crude oil emplacement in the Central Tarim. Al and Si have higher concentrations in the experiments of oxalic acid than of acetic acid under the same pH conditions, suggesting that there exist Al-oxalate and Si-oxalate complexes. Presence of acetate can enhance the activity of Ca and Al, but Al concentrations have not been increased significantly due to formation of small Al-acetate complex during the experiments. Relationships between δD and δ~(18)O in conjunction with chemistry of oilfield waters show that the waters are evaporated connate waters, which subsequently mixed with meteoric water, and were influenced by water-rock interactions such as salt dissolution, dolomitization of calcite, albitization of feldspar. In the Hetianhe Gas Field where salt dissolution took place, δD and δ~(18)O values can be used to trace nicely meteoric water recharge area and flow direction, but TDS can not. Part of the waters have high TDS but very light δD and δ~(18)O. When combined with paleo-topography, or fluid potentials, meteoric water is suggested to flow eastward in the Hetianhe Gas Field, which is the same with the Central Tarim. Whist in the Kuche forland basin, meteoric water may have permeated Cambrian-Ordovician strata. Relationship between ~(87)Sr/~(86)Sr and 1/Sr can be used to indicate migration and mixing of brines from carbonate strata (low ~(87)Sr/~(86)Sr ratio but high Sr content), clastic strata (high ~(87)Sr/~(86)Sr ratio but low Sr content) and crystalline basement (high ~(87)Sr/~(86)Sr ratio and heavy δ~(18)O value). Using this approach, it can be found that ~(87)Sr-depleted brine from Ordovician carbonates have migrated up to and mixed with ~(87)Sr-enriched waters from Silurian and Carboniferous sandstones, and that Silurian brines have mixed with meteoric water. In the Kuche forland basin, brines from the Cambrian and Ordovician carbonates have higher ~(87)Sr/~(86)Sr ratios than those from the overlying sandstones, when combined with chemistry, δ~(15)N and ~3He/~4He ratios of the coexisting natural gases, suggesting that the brines were derived from the basement. There exists some debate on the effect of hydrocarbon emplacement on mineral diagenesis. Case-study from Silurian sandstones in the Central Tarim show that quartz has kept overgrowing secondarily when oil saturation was decreased by meteoric water flushing subsequently to hydrocarbon emplacement. Silicon precipitates on the water-wet quartz surface, leading to decreased Si concentration close to the surface. A Si grads can result in Si diffusion, which supplies Si for quartz overgrowth. Hydrocarbon oxidation-sulfate reduction is an important type of organic-inorganic interaction. Not only can it make secondary alteration of hydrocarbons, but generate H_2S and CO_2 gases which can improve reservoir property. Thermochemical sulfate reduction took place at the temperatures more than 125 ℃ to 140 ℃ in the Cambrian-Ordovician carbonates, the products - H_2S and CO_2 gases migrated up to the Silurian, and precipitated as pyrite and calcite, respectively. The pyrite has an average δ~(34)S value close to those of Ordovician seawater and anhydrite, and calcite has δ~(13)C value as low as -21.5‰. In the Hetianhe Gas Field, sulfate reduction bacteria carried by meteoric water flowing eastward may have preferentially depleted ~(12)C of light hydrocarbon gases, and results in heavier δ~(13)C values of the residual hydrocarbon gases and higher molar CO_2 in the natural gases in the west than in the east. Coexisting pyrite has δ~(34)S values as low as -24.9‰.

中国北方草本植物及表土有机质碳同位素组成

Recently, more and more attention has been paid to stable isotope ratios in terrestrial depositional systems. Among them, δ~(13)C value is mainly determined by the surface vegetation, while vegetation is directly related to climate, therefore, carbon isotope ratio in soil organic matter and pedogenic carbonate has been employed as an important paleoecological indicator. In order to test the paleoecological information extracted from stable isotope ratios in terrestrial depositional systems, it is necessary to study the relationships between δ~(13)C value in standing terrestrial plants and today climate, as well as between δ~(13)C value in modern surface soil organic matter and standing vegetation. Thus, these relationships were studied in this paper by means of analysing δ~(13)C in standing plants and modem surface soil organic matter in North China. The main results and conclusions are presented as following: 1. According to their δ~(13)C values, 40 C-4 species represent about 16% of the 257 plant species sarnpled from the North China. C-4 photosynthesis mainly occurs in Poaceae, Cyperaceae and Chenopidaceae families, and percentage representation of C-4 photosynthesis is up to 56% in Poaceae family. 2. The δ~(13)C values of C-3 plant species in North China vary from -21.7‰ to -32.0‰ with an average of -27.1‰, and 93% focus on the range of -24.0‰ ～ -30.0‰; δ~(13)C values of C-4 plant species in North China are between -10.0‰ ～ -15.5‰ with an average of -12.9‰, and 90% concentrate on the range of -11.0‰ ～ -15.0‰. 3. The δ~(13)C composition of C-3 plant species collected from Beijing, a semi-moist district, mainly vary between -27.0‰ ～ -30.0‰, and the average is -28.7‰; the δ ~(13)C values of plants in the semi-arid district, east and west to the Liu Pan Moutain, focus on the range of-26.0‰ ～ -29.0‰ and -25.0‰ ～ -28.0‰, respectively, with the mean value of -27.6‰ and -26.6‰, respectively; the δ~(13)C composition in the arid district dominantly vary from -24.0‰ to -29.0‰, with the average of -26.2‰, and among them, the δ~(13)C values of C-3 plant species in deserts are often between - 22‰ ～ -24‰; the δ~(13)C values in the cold mountain district concentrate on the range of -24.0‰ to -29.0‰, with the average of -26.3‰. 4. The main range of δ~(13)C composition of C-4 plant species, derived from Beijing, a semi-moist district, are -13.0‰ ～ -15.5‰; the semi-arid district, -11.0‰ ～ -14.0‰; the arid district, -11.0‰ ～ -14.0‰. The mean values of them are -14.0‰, -12.4‰,-12.7‰, respectively. 5. From east to west in North China, δ~(13)C values of C-3 plant species increase with longitude. The correlation between δ~(13)C ratios of C-3 plant species and longitude is linear. Changing temperate and precipitation and changing atmosphere pressure are spossible explanations. 6. Almost all C-3 plant species have the trends that their δ~(13)C values gradually increase with decreasing precipitation, decreasing temperature and increasing altitude. Our results show the increases of the δ~(13)C value by 0.30 ～ 0.45‰, 0.19 ～ 0.27‰ and 1.1 ～ 1.2‰ per 100 mm, I℃ and 1000 m, respectively, for all C-3 plant species together. 7. The δ~(13)C values of all C-3 plant species together and a part of C-3 species show highly significant linear correlation with the mean annual temperature, the mean annual precipitation and the altitude, and the results suggest that they can be used as proxies of these environmental variables, while, those without highly significant correlation, may be not suitable as the proxies. 8. The extent, which of responses of δ~(13)C composition to environmental variables, is different for each C-3 plant specie. 9. The δ~(13)C variations along altitude and longitude may be non-linear for C-4 p1ant species in North China. The mean annual temperature may be not important influential factor, thus, it suggests that the δ~(13)C composition of C-4 plant species may be not suitable as the proxy of the mean annual temperature. The influences of summer temperature on δ~(13)C values are much bigger than that of annual temperature, among them, the influence of September temperature is biggest. The mean annual precipitation may be one of the dominant influential factors, and it shows a highly significant non-linear relationship with δ~(13)C values, and the result indicates that δ~(13) C composition of C-4 plant species can be employed as the proxy of the mean annual precipitation. 10. The variations of δ~(13)C ratios do not show systematic trends along longitude, latitude and altitude for modern surface soil organic in Northwest China. ll. The δ~(13)C ratios of modern surface soil organic do not exhibit systematic patterns with temperature and precipitation in Northwest China, it suggests that, unless soil organic is transferred from pure C-3 or C-4 vegetation, the δ~(13)C composition of soil organic may be not used as proxies of climatic variables. 12. The δ~(13)C values of modem surface soil organic are heavier than that of standing vegetation, and the difference ofrnean δ~(13)C between them is -2.18‰. 13. Without considering the δ~(13)C difference between vegetation and soil organic, as well as the δ~(13)C drift in various enviromnent, we may not obtain the valuable information of C-3, C-4 relative biomass in vegetation. 14. The C-4 biomass contribution in vegetation increase with decreasing latitude, increasing longitude and decreasing altitude in Northwest China. The C-4 biomass almost are zero in those regions north to 38 ° N, or west to 100°E, or above 2400 m. 15. The C-4 relative biomass in vegetation increase with growing temperature and precipitation. and, C-4 plants are rare at those regions where the mean annual temperature is less 4 ℃, or the mean annual precipitation is less 200 mm, and their biomass contribution in vegetation are almost zero. Both the mean annual temperature and the mean annual average precipitation may be the important influential factors of C-4 distribution, but the dominant factors.

藏北措勤盆地白垩纪碳酸盐岩沉积相及缺氧事件响应研究

As a part of Gangdisi-Nianqingtanggula plate, Cuoqin basin (N 29°3O'～33°20'; E 80°～90°) is situated in the west of the Tibet autonomous Region, with an area of 100000 square kilometers. Cretaceous shallow-water carbonate is widely distributed in this basin. Its accumulative thickness is more than 1000 meters. Sedimentary facies of cretaceous shallow-water carbonate and carbon isotope feature are studied in details here. On basis of two main sections researched comprehensively, five facies marks are found. With the combination of Wilson's model and ramp model, a platform-mild slope model are put forward, which is thought to be a comprehensive model for this area. There are three sedimentary circles which are comprised of terrestrial clastic tidal flat and carbonate platform facies in Duoba Member of Duoni Formation. Langshan Formation is mainly comprised of carbonate platform facies. We also studied the carbon isotope features influenced by Cretaceous Aptian-Albian's oceanic anoxic events (OAE). After correlating the δ~(13)C curves of the studied section with that of Peregrina Canyon section in Mexico, we find that there are similar δ~(13)C curves fluctuation styles, namely there is also a δ~(13)C positive excursion in shallow-water carbonate in the studied area, and the degree of δ~(13)C positive excursion in shallow-water carbonate is much higher. There are two main causes which should interpret above δ~(13)C positive excursion feature: on the one hand ,much organic carbon take much 12C off when they are buried with a higher speed during the OAE, which lead to the ~(12)C rise of oceanic total dissolved carbon (TDC),on the other hand, during the OAE there are stratification structures in pale-ocean, in the upper mixed layer with high carbon fixation (HCML). There are so much plankton organisms which absorb much ~(12)C as the ~(13)C of shallow-water carbonate in this layer rise higher. Furthermore, on the basis of the theories of carbonate isotope strata, we suggest that the currently used boundary between Aptian and Albian in the studied area is possibly above the international one, which means the main parts of Duoba Member of Duoni Foramatiom in this area should be belong to Albian in stead of Aptian.

富硫流体的成因与硫酸盐还原作用研究

Origins of H_2S, thiols, thiophenes in natural gases and sulphur-enriched oils are complicated and thus some debates exist on them. The post-doctoral research is based upon oil- and gas-field data. Cases for study include Triassic Jianglingjiang Formation natural gases, Wolonghe Field, Sichuan Basin, Paleozoic oils and bitumen, Central Tarim, gases reserviored nearby Carboniferious - Ordovician unconformity, Hetianhe Field, Tarim Basin and sulphur-enriched oils in Tertiary reserviors in Jinxian Sag, Bohai Bay Basin. We have carried out analyses on the oils and gases for chemistry, δ~(13)C, δ~(34)S, and molecular composition of biomarkers, analyzed authigenetic pyrite forδ~(34)S, formation water for chemistry and δD and δ~(18)O along with petroleum system and burial history analyses, The aims are to assess the origins of the H2S and authigenetic pyrite, to discuss the possibility of reduced sulphur incorporation into hydrocarbons and to determine the mechanisms of hydrocarbon secondary alteration in the above four cases by comparison. The research shows that the reduced sulphur in the four cases is the result of thermochemical and biological sulphate reduction., TSR and BSR, respectively. No evidence indicates an origin of decomposition of organic matter or mantle - derived H2S in the cases. Elevated H_2S contents (up to 32%) in the Triassic Jialingjiang Formation are considered to result from TSR while relatively low H_2S (up to 2000ppm) in the Hetianhe Field resulted from BSR. However, it is not the case for the Central Tarim where relatively low H2S but abundant authigenetic pyrite occurr. Part of the H_2S in the Central Tarim reservoirs has reacted with iron released from clay minerals to precipitate pyrite. Thus, reduced sulphur δ~(34)S and reservoir temperatures rather than the H2S amount are reliable parameters to distinguish between TSR and BSR. TSR in Sichuan Basin Triassic Jialingjiang Formation and Central Tarim Paleozoic reservoirs are showed to take place at more than 125℃. the H2S and authigenetic pyrite have δ~(34)S close to parent anhydrite. In contrast, BSR in the reservoirs near the Carboniferous - Ordovician unconformity in the Hetianhe Field and in the Tertiary in the Jinxian Sag took place at temperatures less than 80℃with sulphide δ~(34)S as light as -24.9‰ and -12.5‰, anhydrite δ~(34)S as heavy as +26‰and +3 5-+40‰, respectively. Chemistry and isotopic composition of the natural gases change as the result of sulphate reduction. It has been observed that relative composition of light hydrocarbon gases is changed along with a rise in H_2S and CO_2. TSR in the Triassic Jialingjiang Formation and BSR in the Hetianhe Field result in a greater degree of preferential depletion of methane than larger molecular hydrocarbon gases. As TSR or BSR proceeds, hydrocarbon gases evolved to heavier carbon isotope as the result of kinetic isotopic fractionation, i.e., selective anaerobic oxidation of ~(12)C. Using the model of residual methane (Whiticar, 1999) to describe the relationship among the proportion of methane oxidation, isotopic shift and fraction factor, about 30% methane is calculated to have been oxidized during BSR in the western part of the Hetianhe Field. From the above, it can be concluded that in the area where H_2S is abundant, empiricalδ~(13)C -Ro relationships do not work. Sulphate reduction results in a rise in sulphur content, gravity and viscosity of an oil as well as changes in δ~(13)C and δ~(34)S. On special conditions, the reduced sulphur from sulphates might be incorporated into oils, i.e., the increasing sulphur is derived from secondarily reduced sulphur. A positive correlative relationship exists between sulphur content and δ~(34)S in the oils in Paleozoic reservoirs in Central Tarim, indicating that enhanced sulphur is ~(34)S-enriched, originated from TSR. The Jinxian oil with the highest sulphur content has the lightest δ~(34)S, suggesting part of the sulphur in the oil is ~(34)S-depleted, originated from BSR. In the Jinxian oil with increasing sulphur content, asphaltenes shows higher content and more negative δ~(13)C, and saturates shows evidence of biodegradetion and a decreasing content and a positive δ~(13)C shift. Thus, asphaltenes have δ~(13)C values closer to saturates. All the above indicate that the reduced sulphur has been incorporated into biodegradated saturates to generate new asphaltenes with relatively light δ~(13)C of saturates. Thiols and thiophenes in natural gases in the Triassic Jialingjiang Formation may result from reaction of H_2S with hydrocarbon. In the Jialingjiang Formation hydrocarbon gases are dominated by methane thus have a high dryness coefficient and thiols are showed to be positively related to H_2S content, suggesting that the thiols may result from H_2S reaction with short chain hydrocarbons. In contrast, high thiophenes occur in wet gases in Jurassic reservoirs with their source rock from sulphur - depleted type I kerogen, indicating that thiophenes may be a product of reaction of H2S with longer chain hydrocarbons.

华南震旦纪-寒武纪两期成磷事件及其地球动力学意义

Phosphorus is an important biological and ecological element that to a certain degree constrains ecological environment and nutrient (including carbon) cycling. Marine sedimentary phosphorites are the principal phosphorus supply of the mankind. In the eastern to southern margins of the Yangtze Craton, South China, there are two phosphogenetic events at the Doushantuo stage of the Late Sinian and the Meishucun stage of the Early Cambrian respectively, corresponding two explosion events of life across the Precambrian\Cambrian boundary. Phosphorus ores from the Sinian and Cambrian phosphate in South China can be classified roughly into two categories, namely, grained and non-grained phosphorites. Grained phosphorites, hosted in dolostone type of phosphogenetic sequences and with larger industrial values, occur mainly in margins of the Upper Yangtze Platform, formed in shallow-water environments with high hydraulic energy and influenced by frequent sea-level change. Non-grained phosphorites, hosted principally in black-shale type of phosphogenetic sequences and with smaller industrial values, are distributed mainly in the Jiangnan region where deeper-water sub-basins with low hydraulic energy were prevailing at the time of phosphogenesis. Secular change ofδ~(13)C, δ~(18) O, ~(86)Sr/~(87)Sr values of carbonates from Sinian and Cambrian sequences were determined. A negative abnormal ofδ~(13)C, δ~(18)O values and positive abnormal of 86Sr/87Sr values from the fossiliferous section of the Lowest Cambrian Meishucun Formation implies life depopulation and following explosion of life across the PrecambriamCambrian boundary. Based on a lot of observations, this paper put forward a six-stage genetic model describing the whole formational process of industrial phosphorites: 1) Phosphorus was transported from continental weathering products and stored in the ocean; 2) dissolved phosphates in the seawater were enriched in specific deep seawater layer; 3) coastal upwelling currents took this phosphorus-rich seawater to a specific coastal area where phosphorus was captured by oceanic microbes; 4) clastic sediments in this upwelling area were enriched in phosphorus because of abundant phosphorus-rich organic matters and because of phosphorus absorption on grain surfaces; 5) during early diagenesis, the phosphorus enriched in the clastic sediments was released into interstitial water by decomposition and desorption, and then transported to the oxidation-reduction interface where authigenic phosphates were deposited and enriched; 6) such authigenic phosphate-rich layers were scoured, broken up, and winnowed in shallow-water environments resulting in phosphate enrichment. The Sinian-Cambrian phosphorites in South China are in many aspects comparable with coastal-upwelling phosphorites of younger geological ages, especially with phosphorites from modern coastal upwelling areas. That implies the similarities between the Sinian-Cambrian ocean and the modern ocean. Although Sinian-Cambrian oceanic life was much simpler than modern one, but similar oceanic planktons prevail, because oceanic planktons (particularly phytoplanktons) are crucial for phosphate enrichment related to coastal upwelling. It implies also a similar seawater-layering pattern between the Sinian-Cambrian ocean and the modern ocean. The two global phosphate-forming events and corresponding life-explosion events at the Sinian and Cambrian time probably resulted from dissolved-phosphate accumulation in seawater over a critical concentration during the Earth's evolution. Such an oceanic system with seawater phosphorus supersaturation is evidently unstable, and trends to return to normal state through phosphate deposition. Accordingly, this paper put forward a new conception of "normal state <=> phosphorus-supersaturation state" cycling of oceanic system. Such "normal state <=> phosphorus-supersaturation state" cycling was not only important for the three well-known global phosphate-forming events, also related to the critical moments of life evolution on the Earth. It might be of special significance. The favorable paleo-oceanic orientation in regard to coastal-upwelling phosphorite formation suggests a different orientation of the Yangtze Craton between the Sinian time and the present time (with a 135° clockwise difference), and a 25° anti-clockwise rotation of the Yangtze Craton from late Sinian to early Cambrian. During the Sinian-Cambrian time, the Yangtze Craton might be separated from the Cathaysia Block, but might be still associated with the North China Craton.

贵州喀斯特山区植物叶片碳同位素组成研究

通过测定贵州喀斯特山区灌丛12 种主要植物叶片的δ13 C 值,研究了该区植物叶片碳同位素组成特征,以及种间、生境差异和时空变化特征。研究结果表明:该区植物叶片的碳同位素组成的变化范围为- 26. 98 ‰～ - 29. 15 ‰,平均值为- 28. 14 ‰。研究区δ13C 值的分布相对均匀,除高于我国热带雨林区植物外,低于其它地区。研究结果还表明,种间碳同位素组成存在较大的差异。生境的变化对蕨的碳同位素组成影响较大,而对渐尖毛蕨、盐肤木、火棘、马桑影响较小。盐肤木、渐尖毛蕨、云南鼠刺、火棘叶片的δ13C 值从生长初期到末期有降低的趋势,但降低的幅度存在差异。植物的δ13 C 值随小尺度海拔的变化规律与随大尺度海拔变化的规律一致,都是随着海拔的增加δ13C 值增大,但不同植物种间变化的幅度是不一样的。

单种属泥炭纤维素碳稳定同位素组成与全新世青藏高原东部西南季风变化

泥炭的形成和积累主要受控于气候，其次是地质、地貌和水文等因素。作为一种重要和理想的气候信息载体，泥炭己经与冰芯、海洋及湖泊沉积、黄土堆积、洞穴碳酸盐沉积、树轮和珊瑚礁等其它类型的自然地质档案一样，逐渐为国内外致力于古气候变化研究的学者所接受，并将其重点应用于全新世以来气候变化信息的提取。本研究在已有的泥炭混合植物残体纤维素碳稳定同位素记录青藏高原东部地区气候信息的基础上，首次提取泥炭中单一种属植物残体一木里苔草（Calexmulieensis）纤维素，测定其碳稳定同位素，并以其时间序列作为一种新的西南季风代用指标，揭示该区域全新世以来气候变化。研究表明：1．木里苔草的碳稳定同位素时间序列是西南季风强度变化的敏感代用指标。约11800～11加0 cal aBP期间，木里苔草纤维素的613C记录处于最大值，表明该时段西南季风活动鼻弱，气候干冷，对应于普遍发生并存在的新仙女木事件；它清晰地指示了该区全新世的下限年龄为约11200 cal aBP（14c年龄约9900aB玲从约11200 oal aBP起该区迅速进入湿暖的全新世阶段，季风活动迅速增强；在约10800～5500 cal aBP期间，季风总体保持在强盛状态，但其间有4次突然减弱，气候变干冷；约从5500 cala即起季风活动在波动中逐渐减弱，其中有4次减弱最为明显。2．木里苔草纤维素碳同位素所记录的犯000年以来的所有9次西南季风活动的突然减弱与同时期北大西洋发生的冰力｝漂移碎屑沉积物事件（IRD事件）一一对应。这种密切的相关关系表明，西南季风强度的波动可能是对全球气候变化特别是对海洋热盐环流引起的地球南北方气撇动变化的响应。3．木里苔草纤维素碳稳定同位素所指示的西南季风有952，乓57，475，312，211和77年等一系列周期。其中557年和77年两个周期分别与北大西洋深层海水环流的550年的周期和76年的气候周期非常吻合。这表明西南季风与北大西洋气候间有很好的相关关系。由于557年和77年的季风周期又都分别类似于53。年和80年的太阳活动周期，这表明太阳活动可能对西南季风和北大西洋气候间的联系有着影响。4．红原泥炭木里苔草纤维素和泥炭混合纤维素别3c时间序列在千年至万年时间尺度上的变化趋势很相近。两种代用记录都一致反映了冰后期的气候变化，即均指示西南季风强度变化可分为三个明显的大阶段。这说明它们对过去12000年的西南季风变化具有相同的响应。对于目前经过较详细研究的那些全球大范围发生的突然气候变化事件，木里苔草纤维素δ~(13)C代用记录与泥炭混合纤维素δ~(13)C代用记录一样，都有相同的响应，但是，相对于泥炭中单一的木里苔草敏感地记录到历次北大西洋I劝事件而言，泥炭混合纤维素δ~(13)C记录对其中的几次突然气候变化事件似乎没有表现出明显的响应。这个结果表明对数百年尺度的突然气候变化，木里苔草纤维素比混合纤维素的酬3c指标似乎要更敏感一点。因此，在能获得足够数量的单种植物·残体的情况下，单种植物残体纤维素的δ~(13)C指标有很好的使用价值。