无机成因油气及其资源前景

地幔和地核中大量的碳和氢以及地幔深处的甲烷、二氧化碳等提供了无机成因气体的物质基础,近年来地球化学方法的应用给有机和无机成因天然气提供了可靠的判别依据,主要有⑴无机成因甲烷的δ1 3C1≥-30.0‰⑵无机成因烷烃气体具有负碳同位素系列,即δ1 3C1δ1 3C2δ1 3C3δ1 3C4⑶R/Ra0.5,δ1 3C1-δ1 3C20为无机成因烷烃气⑷CH4/3He≤106是无机成因烷烃气(甲烷)。这些判别指标的提出有效地指导了无机成因天然气的勘探实践。目前在我国东部已发现了35个无机成因的二氧化碳气藏,并首次发现无机成因烷烃气藏—昌德气藏,资源潜力巨大,因此应积极开展无机成因气的勘探和开发,使这一产量巨大的油气后备领域早日得到利用。     

Using hourly measurements to explore the role of secondary inorganic aerosol in PM2.5 during haze and fog in Hangzhou,China

This paper explores the role of the secondary inorganic aerosol （SIA） species ammonium,NH4＋,nitrate,NO3-,and sulfate,SO24-,during haze and fog events using hourly mass concentrations of PM2.5 measured at a suburban site in Hangzhou,China.A total of 546 samples were collected between 1 April and 8 May 2012.The samples were analyzed and classified as clear,haze or fog depending on visibility and relative humidity （RH）.The contribution of SIA species to PM2.5 mass increased to ～50％ during haze and fog.The mass contribution of nitrate to PM2.5 increased from 11％ during clear to 20％ during haze episodes.Nitrate mass exceeded sulfate mass during haze,while near equal concentrations were observed during fog episodes.The role of RH on the correlation between concentrations of SIA and visibility was examined,with optimal correlation at 60％-70％ RH.The total acidity during clear,haze and fog periods was 42.38,48.38 and 45.51 nmol m-3,respectively,indicating that sulfate,nitrate and chloride were not neutralized by ammonium during any period.The nitrate to sulfate molar ratio,as a function of the ammonium to sulfate molar ratio,indicated that nitrate formation during fog started at a higher ammonium to sulfate molar ratio compared to clear and haze periods.During haze and fog,the nitrate oxidation ratio increased by a factor of 1.6-1.7,while the sulfur oxidation ratio increased by a factor of 1.2-1.5,indicating that both gaseous NO2 and SO2 were involved in the reduced visibility.     

Nutrients in an oligotrophic boundary current: Evidence of a new role for the Leeuwin Current

New observations along the continental shelf of Western Australia provide a novel explanation for the established ∼60 years relationship between Leeuwin Current (LC) strength and greater winter nitrate concentrations at 32°S plus the inter-annual variation in the magnitude of the annual, shelf-scale, phytoplankton bloom. The potential source of dissolved nitrogen to support the annual shelf scale phytoplankton bloom was identified as thin layers of an unprecedented areal extent, nitrate concentration and shallow nature that were observed off the northwest of Australia. We propose that the dissolved inorganic nitrogen (DIN) in these layers enters the LC at depth and then enters the euphotic zone via by three mechanisms: instability that results in a warm core eddy, cooling that deepens the surface mixed layer and shallowing of the thin layer. During the onset of the annual phytoplankton bloom along the west coast of Australia from 22°S to 34°S the poleward flowing LC was clearly evident as a surface intensified ocean boundary current transporting warmer, lower-salinity, greater-silicate waters in a shallow mixed layer rapidly southward. Between 24 and 26°S the core of the LC was present as a 50–100 m deep layer over one or more thin layers, 15–50 m thick, with high nitrate and low dissolved oxygen (DO). These layers were of lower salinity, cooler water with markedly reduced DO, high nitrate concentrations and distinct nitrate:silicate (NO₃:Si(OH)₄) nutrient ratios. As the LC flowed south it cooled and deepened thereby entraining the thin layers of high nitrate water into the euphotic zone. The LC also formed large (greater than 100 km diameter) warm core eddies with a deep surface mixed layer that also entrained nitrate from these thin layers. In some locations as far south as 32°S the LC was still present with the thin layer of high nitrate intact but now within the euphotic zone. Thus, the available evidence suggests the LC arises under conditions that favour rapid and shallow nitrification. This nitrification fuels a shelf-scale bloom on a downwelling favourable coast. Depending upon the rate of nitrification the source of the particular organic matter may be local or delivered from the tropics via horizontal advection in a subsurface layer of the LC.     

STUDY ON DETERMINATION OF DIC IN SEAWATER BY COULOMETRIC METHOD

lareODUcrIONThetotalcarbondi0xideisandriportantparametrforestirnatingthespatiotem0ralinorganiccarbontransport,andanthropogeniccarb0ndi0xideincreasesintheoonn.Ap~coulomericednique(MethodG0fASTMD5l3-82)formeasuringDICinanwaterdevelopedbyJohnsonetal.(l985)istheshipkoardmehodchosenfortheglobeocanicinofganiccarb0nsurveyt0bemadeinconjunCtionwiththeW0riddrinCirmlationExperirnentWorklHydrographicProgram(WOCEWHP)andtheJointGobal~nFluxStudy(JGOFS)program(Catherine,G.etal.,l993).Thecruxof…     

Pore Types and Quantitative Evaluation of Pore Volumes in the Longmaxi Formation Shale of Southeast Chongqing,China

The common microscale to nanoscale pore types were introduced and divided into organic and inorganic pores to estimate their contributions to porosity in the Lower Silurian Longmaxi Formation shale of southeast Chongqing. Following the material balance principle, the organic porosity values, which changed with formation subsidence and thermal evolution, were calculated using chemical kinetics methods and corrected via the organic porosity correction coefficient, which was obtained from field emission scanning electron microscopy. Grain density values were determined using the contents and true densities of compositions in the shale samples. The total porosity was calculated based on the grain and bulk densities. The inorganic porosity was determined from the difference between the total porosity and organic porosity at the same depth. The results show that inorganic pores mainly contain microfractures, microchannels, clay intergranular pores, intercrystalline pores and intracrystalline pores in the Lower Silurian Longmaxi Formation shale of southeast Chongqing. Organic pores mainly include organopore and fossil pore. The total porosity, organic porosity and inorganic porosity of organic-rich shale samples can be quantitatively evaluated using this method. The total porosity, organic porosity and inorganic porosity values of the Longmaxi Formation shale samples from the well Py1 in southeast Chongqing lie in 2.75%–6.14%, 0.08%–2.52% and 1.41%–4.92% with average values of 4.34%, 0.95% and 3.39%, respectively. The contributions of the inorganic pores to the total porosity are significantly greater than those of the organic pores.     

Carbonate and carbon isotopic evolution of groundwater contaminated by produced water brine with hydrocarbons

The major ionic and dissolved inorganic carbon (DIC) concentrations and the stable carbon isotope composition of DIC (δ¹³C_DIC) were measured in a freshwater aquifer contaminated by produced water brine with petroleum hydrocarbons. Our aim was to determine the effects of produced water brine contamination on the carbonate evolution of groundwater. The groundwater was characterized by three distinct anion facies: HCO₃⁻-rich, SO₄²⁻-rich and Cl⁻-rich. The HCO₃⁻-rich groundwater is undergoing closed system carbonate evolution from soil CO_2(g) and weathering of aquifer carbonates. The SO₄²⁻-rich groundwater evolves from gypsum induced dedolomitization and pyrite oxidation. The Cl⁻-rich groundwater is contaminated by produced water brine and undergoes common ion induced carbonate precipitation. The δ¹³C_DIC of the HCO₃⁻-rich groundwater was controlled by nearly equal contribution of carbon from soil CO_2(g) and the aquifer carbonates, such that the δ¹³C of carbon added to the groundwater was −11.6‰. In the SO₄²⁻-rich groundwater, gypsum induced dedolomitization increased the ¹³C such that the δ¹³C of carbon added to the groundwater was −9.4‰. In the produced water brine contaminated Cl⁻-rich groundwater, common ion induced precipitation of calcite depleted the ¹³C such that the δ¹³C of carbon added to the groundwater was −12.7‰. The results of this study demonstrate that produced water brine contamination of fresh groundwater in carbonate aquifers alters the carbonate and carbon isotopic evolution.     

中国荒漠C4木本植物和土壤无机固碳研究回顾与展望

碳是贯穿自然和社会的首要元素之一,碳循环是自然和社会系统的重要纽带。陆地生态系统的自然固碳途径有2种,一种是植物碳同化,另一种是土壤碳同化,人们一直关注植物的有机固碳,对于土壤的无机固碳重视不够。本文回顾了中国荒漠区固碳能力强的C₄木本植物和土壤无机固碳研究进展。通过解剖结构观察、δ¹³C值和气体交换特征全面分析得出,荒漠植物梭梭（Haloxylon ammodendron）和沙拐枣（Calligonum mongolicum）为典型的C₄木本植物,梭梭同化枝有大量的含晶细胞,沙拐枣同化枝有大量的黏液细胞。干旱区荒漠的非生物固碳能力至今缺乏合理解释。通过对戈壁、沙漠和壤质荒漠土壤无机碳密度和碳储量分析,提出了土壤碳同化（soil carbon assimilation）概念,并给出了土壤碳同化途径的3个阶段,解释了土壤无机固碳这一现象;与植物碳同化比较,土壤碳同化是荒漠固碳的主要途径。最后,展望了荒漠C₄木本植物和土壤碳同化的研究方向及对中国2060年前实现碳中和目标的可能贡献。     

Fractions and Bioavailability of Soil Inorganic Phosphorus in the Loess Plateau of China under Different Vegetations

Plants play an important role in soil phosphorus nutrition. However, the effect of plants on phosphorus nutrition in soils of the Loess Plateau of China is not well understood. This study was conducted to reveal the relationships between plants and phosphorus’ fractions and availability in the Loess Plateau of China. Twenty-two plant communities were surveyed and soil samples under different plant canopies were collected for the determination of soil properties and inorganic phosphorus fractionation. The results showed that Leguminosae and Lilaceae reduced pH and increased organic matter, cation exchange capacity, total and Olsen phosphorus in soils under their canopies, while Labiatae and Rosaceae increased pH and decreased organic matter, cation exchange capacity, total and Olsen phosphorus in soils under their canopies. The contents of Ca2P, Ca8P, Al-P and Fe-P were highly related with soil Olsen phosphorus. They were all higher in soils under Leguminosae and Lilaceae and lower in soils under Labiatae and Rosaceae. The results of this study indicate that Leguminosae and Lilaceae improved phosphorus nutrition in soils, yet Labiatae and Rosaceae impeded the improvement of phosphorus nutrition in soils under their canopies, which will be of more help to instruct vegetation restoration in the region and provide information for soil development.     

Melt and fluid inclusion evidence for a genetic relationship between magmatism in the Shuangliao volcanic field and inorganic CO2 gas reservoirs in the southern Songliao Basin,China

We have studied melt and fluid inclusions in minerals from alkali basalts, mantle xenoliths, and dawsonite-bearing sandstones from the Shuangliao volcanic field in southern Songliao Basin, Northeast China. The inclusions have been investigated using petrographic, geochemical, and laser Raman spectroscopic techniques. Volcanic rocks of the Shuangliao field are predominantly alkali olivine basalts that contain rare mantle xenoliths. Silicate melt and fluid inclusions are common in both olivine phenocrysts and the mantle xenoliths. The fluid inclusions are mainly composed of CO₂ with small amounts of CO, CH₄, N₂, and H₂O, which is consistent with an upper mantle origin. CO₂ gas reservoirs in the southern Songliao Basin are mostly derived from a mantle–magmatic source. Coeval fluid-inclusion homogenization temperatures, coupled with the thermal burial history, show that the CO₂ gas reservoirs in the southern Songliao Basin are Cenozoic (40–63 Ma) and coeval with the magmatism in the Shuangliao volcanic field. Despite the relatively small scale of this volcanic activity, it released large amounts of CO₂. Much of the magma was not erupted, and CO₂- and H₂O-rich magma was probably intruded into the basin along deep faults, acting as a major source of inorganic CO₂ gas in the southern Songliao Basin.     

Geochemistry of Holocene salt marsh and tidal flat sediments on a barrier island in the southern North Sea (Langeoog,North‐west Germany)

The barrier islands of the southern North Sea were formed during the Holocene sea‐level rise. These islands form part of a highly dynamic environment whose evolution continues today. Subjected to sea‐level changes, tides and storm events, the sedimentary record reflects processes occurring under varying energy conditions. This article presents geochemical, mineralogical and diatom investigations carried out in the salt marsh of the East Frisian barrier island of Langeoog, which is re‐exposed to a rising sea‐level due to de‐embankment. The major aim of this study is to improve the knowledge of the sedimentological and geochemical development of these deposits under the influence of sea‐level rise, with a special focus on the geochemistry and distribution of heavy mineral‐associated elements. Correlation diagrams between FeO, TiO₂ and MnO, as well as ternary plots (Al₂O₃–SiO₂–Zr or TiO₂), clearly indicate the variable appearance of heavy minerals in different lithological facies, comprising marsh soil, mixed and sand flat, and relocated beach sands. A dominating abundance of ilmenite followed by zircon, garnets and some other heavy minerals is evidenced by Scanning Electron Microscope‐Energy Dispersive X‐ray measurements. The data presented here suggests that these geochemical proxies are useful tools for characterizing depositional energy conditions. Increasing depositional energy is evident for the lithological units in the following order: marsh soil, mixed flat, sand flat and relocated beach sand. The energetic conditions during sediment deposition, as well as the sedimentary history, are confirmed by diatom analyses as an additional independent indicator. Depending on source rock composition, the geochemical parameters used in this study may also help to investigate depositional energy regimes of other siliciclastic sedimentary systems.