The thermal structure of the Dvurechenskii mud volcano and its implications for gas hydrate stability and eruption dynamics

The sediment temperature distribution at mud volcanoes provides insights into their activity and into the occurrence of gas hydrates. If ambient pressure and temperature conditions are close to the limits of the gas hydrate stability field, the sediment temperature distribution not only limits the occurrence of gas hydrates, but is itself influenced by heat production and consumption related to the formation and dissociation of gas hydrates. Located in the Sorokin Trough in the northern Black Sea, the Dvurechenskii mud volcano (DMV) was in the focus of detailed investigations during the M72/2 and M73/3a cruises of the German R/V Meteor and the ROV Quest 4000 m in February and March 2007. A large number of in-situ sediment temperature measurements were conducted from the ROV and with a sensor-equipped gravity corer. Gas hydrates were sampled in pressurized cores using a dynamic autoclave piston corer (DAPC). The thermal structure of the DMV suggests a regime of fluid flow at rates decreasing from the summit towards the edges of the mud volcano, accompanied by intermittent mud expulsion at the summit. Modeled gas hydrate dissociation temperatures reveal that the gas hydrates at the DMV are very close to the stability limits. Changes in heat flow due to variable seepage rates probably do not result in changes in sediment temperature but are compensated by gas hydrate dissociation and formation.     

Winkler's method overestimates dissolved oxygen in seawater: Iodate interference and its oceanographic implications

Dissolved oxygen in seawater has been determined by using the Winkler's reaction scheme for decades. An interference in this reaction scheme that has been heretofore overlooked is the presence of naturally occurring iodate in seawater. Each mole of iodate can result in an apparent presence of 1.5 mol of dissolved oxygen. At the concentrations of iodate in the surface and deep open ocean, it can lead to an overestimation of 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 of oxygen in these waters respectively. In coastal and inshore waters, the effect is less predictable as the concentration of iodate is more variable. The solubility of oxygen in seawater was likely overestimated in data sources that were based on the Winkler's reaction scheme for the determination of oxygen. The solubility equation of García and Gordon [Garcia H.E., Gordon, L.I., 1992. Oxygen solubility in seawater: Better fitting equations. Limnol. Oceanogr. 37, 1307–1312] derived from the results of Benson and Krause [Benson, F.B., Krause, D. Jr., 1984. The concentration and isotopic fractionation of oxygen dissolved in freshwater and seawater in equilibrium with the atmosphere. Limnol. Oceanogr. 29, 620–632] is free from this source of error and is recommended for general use. By neglecting the presence of iodate, the average global super-saturation of oxygen in the surface oceans and the corresponding efflux of oxygen to the atmosphere both have been overestimated by about 8%. Regionally, in areas where the degree of super-saturation or under-saturation of oxygen in the surface water is small, such as in the tropical oceans, the net air–sea exchange flux can be grossly under- or overestimated. Even the estimated direction of the exchange can be reversed. Furthermore, the presence of iodate can lead to an overestimation of the saturation anomaly of oxygen in the upper ocean attributed to biological production by 0.23 ± 0.07%. AOU may have been underestimated by 0.52 ± 0.15 and 0.63 ± 0.05 μmol kg^− 1 in the surface mixed layer and deep water, while preformed phosphate and preformed nitrate may have been overestimated by 0.004 ± 0.001 and 0.06 ± 0.02 μmol kg^− 1 in the surface mixed layer, and 0.005 ± 0.0004 and 0.073 ± 0.006 μmol kg^− 1 in the deep water. These are small but not negligible corrections, especially in areas where the values of these parameters are small. At the increasing level of sophistication in the interpretation of oxygen data, this source of error should now be taken into account. Nevertheless, in order to avoid confusion, an internationally accepted standard needs to be adopted before these corrections can be applied.     

柴达木盆地烃蚀变矿物高光谱遥感识别研究

高光谱遥感识别烃蚀变矿物可用于探测油气烃类微渗漏和定位地下油气藏.以有天然气分布的柴达木盆地东部三湖地区为研究区,对Hyperion高光谱数据进行重采样处理,克服了目标识别矿物不明显和传感器低信噪比的影响.通过确定烃蚀变矿物高光谱遥感探测的指示标志,采用线性光谱(SAM)拟合与光谱匹配(SAM)相结合的方法确定了影像端元对应的矿物组分.识别结果表明,合理缩减影像波段数和确定影像端元的方法,能有效提高烃蚀变矿物的高光谱遥感识别精度.     

古新世—始新世最热事件对地球表层循环的影响及其触发机制

古新世—始新世最热事件（PETM, Paleocene Eocene Thermal Maximum）是发生在古新世—始新世交界时的一次全球性的气候突变事件。它造成了大洋环流模式的突然倒转和海水盐度、大气湿度的迅速上升。海洋表层生态系统和陆地生态系统生产力迅速上升,许多属种的植物、动物、微生物生活范围向高纬区扩大;大洋底栖微生物发生集群灭绝。现代哺乳动物的主要属种（灵长类、奇蹄类及偶蹄类）产生,哺乳动物演化进程发生重大改变。地球表层碳循环系统发生不同程度的碳同位素负偏移,全球碳循环系统发生大规模搅动。对于PETM的触发机制,主流的观点认为是海底天然气水合物突然释放造成巨量甲烷迅速进入表层系统引发的碳循环系统内部反馈。而对于甲烷释放的原因,又存在着减压释放和热释放两种解释;此外还有科学家用岩浆作用和地外星体撞击来解释PETM的发生。     

Gas generation and expulsion characteristics of Middle–Upper Triassic source rocks,eastern Kuqa Depression,Tarim Basin,China: implications for shale gas resource potential

Frontier exploration in the Kuqa Depression, western China, has identified the continuous tight-sand gas accumulation in the Lower Cretaceous and Lower Jurassic as a major unconventional gas pool. However, assessment of the shale gas resource in the Kuqa Depression is new. The shale succession in the Middle–Upper Triassic comprises the Taliqike Formation (T₃t), the Huangshanjie Formation (T₃h) and the middle–upper Karamay Formation (T_2–3k), with an average accumulated thickness of 260 m. The high-quality shale is dominated by type III kerogen with high maturity and an average original total organic carbon (TOC) of about 2.68 wt%. An improved hydrocarbon generation and expulsion model was applied to this self-contained source–reservoir system to reveal the gas generation and expulsion (intensity, efficiency and volume) characteristics of Middle–Upper Triassic source rocks. The maximum volume of shale gas in the source rocks was obtained by determining the difference between generation and expulsion volumes. The results indicate that source rocks reached the hydrocarbon expulsion threshold of 1.1% VR and the hydrocarbon generation and expulsion reached their peak at 1.0% VR and 1.28% VR, with the maximum rate of 56 mg HC/0.1% TOC and 62.8 mg HC/0.1% TOC, respectively. The volumes of gas generation and expulsion from Middle–Upper Triassic source rocks were 12.02 × 10¹² m³ and 5.98 × 10¹² m³, respectively, with the residual volume of 6.04 × 10¹² m³, giving an average gas expulsion efficiency of 44.38% and retention efficiency of 55.62%. Based on the gas generation and expulsion characteristics, the predicted shale gas potential volume is 6.04 × 10¹² m³, indicating a significant shale gas resource in the Middle–Upper Triassic in the eastern Kuqa Depression.     

聚四氟乙烯平板型气态膜回收淡盐水中氯气

本文以离子膜电解氯化钾制取碳酸钾工艺产生的淡盐水为原料,系统地研究了聚四氟乙烯平板型气态膜回收氯过程中膜性能和次氯酸钠水溶液的制备。初步研究表明,次氯酸钠含量大于100g/L,氢氧化钠有效利用率为90％;聚四氟乙烯膜有传质快、对离子截留性能好、使用寿命长等优点,在工业上有较好的应用前景。     

Meteorology and haze structure during AGASP-II,Part 1: Alaskan Arctic flights, 2–10 April 1986

The second Arctic Gas and Aerosol Sampling Program (AGASP-II) was conducted across the Alaskan and Canadian Arctic in April 1986, to study the in situ aerosol, and the chemical and optical properties of Arctic haze. The NOAA WP-3D aircraft, with special instrumentation added, made six flights during AGASP-II. Measurements of wind, pressure, temperature, ozone, water vapor, condensation nuclei (CN) concentration, and aerosol scattering extinction (b_sp) were used to determine the location of significant haze layers. The measurements made on the first three flights, over the Arctic Ocean north of Barrow and over the Beaufort Sea north of Barter Island, Alaska are discussed in detail in this report of the first phase of AGASP II. In the Alaskan Arctic the WP-3D detected a large and persistent region of haze between 960 and 750 mb, in a thermally stable layer, on 2, 8, and 9 April 1986. At its most dense, the haze contained CN concentrations >10,000 cm^–3 and b_sp of 80×10^–6 m^–1 suggesting active SO₂ to H₂SO₄ gas-to-particle conversion. Calculations based upon observed SO₂ concentrations and ambient relative humidities suggest that 10⁴–10⁵ small H₂SO₄ droplets could have been produced in the haze layers. High concentrations of sub-micron H₂SO₄ droplets were collected in haze. Ozone concentrations were 5–10 ppb higher in the haze layers than in the surrounding troposphere. Outside the regions of haze, CN concentrations ranged from 100 to 400 cm^–3 and b_sp values were about (20–40)×10^–6 m^–1. Air mass trajectories were computed to depict the air flow upwind of regions in which haze was observed. In two cases the back trajectories and ground measurements suggested the source to be in central Europe.     

Biological marker compounds as indicators of the depositions! history of the Maoming oil shale

The Eocene Maoming oil shale from Guangdong Province occurs as a laterally uniform stratigraphic section, typically 20–25 m thick, from which the aliphatic hydrocarbon constituents of six representative samples were investigated using GC and C-GC-MS. The sediments evaluated included the basal lignite, a vitrinite lens from the overlying claystone, and four intervals from the massive oil shale bed. As expected, the lignite and vitrinite differ markedly from the oil shales. The lignite is dominated by bacterial hopanoids and components of higher plant origin, including C₂₉ steroids and triterpenoids such as oleanenes. Visually, the oil shale samples show corroded and degraded phytoclasts, spores, wispy particles of fluorescent organic material attributable to dinoflagellates and, especially in the uppermost sample, colonial algal bodies. The distributions of biological markers in the oil shales show many features in common, notably a dominance of dinoflagellate-derived 4-methylsteroids, and a significant proportion of higher-plant derived n-alkanes with marked odd-over-even carbon number predominance. Overall, they exhibit several features that resemble characteristics of the Messel shale. The hydrocarbons of the lowest shale horizon suggest that there may have been a gradual transition between deposition of the original peat and the subsequent oil shales. The aliphatic hydrocarbons of the uppermost shale are dominated by a number of C₃₁ and C₃₃ botryococcane homologues and other unusual branched alkanes possibly derived from green algae. All of the samples are immature. Overall, molecular and microscopic examination of the stratigraphic succession of the Maoming oil shale suggests a shallow, lacustrine environment within which peats were deposited. This lake subsequently deepened to support abundant algal populations, especially dinoflagellates, culminating in a dominance of botryococcoid algae.     

Determination of nitrophenols,diaminotoluenes, and chloroaromatics in ammunition wastewater

Methods for the determination of three compound classes, i. e. diaminotoluenes, nitrophenols, and chloroaromatics in groundwater of a former ammunition plant are reported. Diaminotoluenes were extracted by discontinuous liquid/liquid-, nitrophenols by continuous liquid/liquid-extraction using dichloromethane, and chloroaromatics by solid-phase extraction. These compound classes may be analyzed by gas chromatography (GC) or gas chromatography coupled to mass spectrometry (GC/MS) without derivatization or after derivatization with N-methyl-bis(trifluoroacetamide) (MBTFA) or heptafluorobutyric anhydride (HFBA) in the case of diaminotoluenes and HFBA or acetic anhydride in the case of nitrophenols. An atomic emission detector (AED) coupled to a gas chromatograph may be employed for the analysis of chloroaromatics. High selectivity can be achieved using the characteristic wavelengths of chlorine. A variety of these compounds were identified and quantified in a groundwater sample from the former ammunition plant Elsnig (Saxony, Germany). Concentrations were in the lower ppb range. Thus, dichlorobenzenes which may have been used as substituents at the end of World War II could be identified in groundwater samples at this site.     

Direct and Indirect pCO2 Measurements in a Wide Range of pCO2 and Salinity Values (The Scheldt Estuary)

Recent improvements in both Infra-red spectroscopy and equilibrator techniqueshave allowed to determine, for the first time, pCO₂using simultaneously and continuously both the direct and indirect methods in an estuary where pCO₂ values range from 500 to 8500 atm and salinity from 0 to 30. Our results show that both methods are in excellent agreement in the wholeestuary (r² = 0.999, n = 1075, p < 0.0001). Thus, the NBS (US National Bureau of Standards) scale, although inadequate for seawater samples, is appropriate for estuarine waters and can be applied with confidence to calculate pCO₂.