Distributional characteristics of DOC in the central Equatorial Pacific

Distributions of dissolved organic carbon (DOC) as determined by high temperature catalytic oxidation (HTCO) method, are reported for 5 stations located from 15°N to 5°S along the transect of 180° in the central Equatorial Pacific. Vertical profiles of DOC suggest that levels of DOC in the photic layer at a given station are dependent on the vertical stability of the water column and meridional currents in the central Equatorial Pacific. Concentrations of DOC determined by the HTCO method in the northern North to Equatorial Pacific and those of total organic carbon (TOC) determined by Wet Chemical Oxidation (WCO) method during the GEOSECS Pacific cruises indicated that DOC determined by both methods, taken together with the levels of DOC in the surface water, showed clear meridional differences in the areas from north of 40°N to the equatorial region in the Pacific: values were low at high latitudes, namely, in productive areas, but high at low latitudes, namely, in oligotrophic areas, even though the values of DOC determined by the two methods were different.     

The measurement of the volatile organic fraction of the TOC in seawater

A method based on a dynamic head-space extraction and high-temperature oxidation of the trapped organic matter is described for the determination of the volatile organic carbon (VOC) concentration in seawater. The VOC concentrations in various geographic regions have been measured and calculated as a fraction of the total organic carbon (VOC/TOC). The VOC concentrations ranged from 15–60 μg C/liter in most oceanic areas. This volatile component was found to be a small fraction (1.5–6%) of the TOC. The VOC concentrations are highest in coastal regions and in the surface zone while the VOC/TOC ratio is relatively constant with depth and location. The volatile organic components may be important to the cycling of organic matter in sea water and the dynamics of this role have been postulated.     

化学发光动力学法分析海水总有机碳研究与实现

提出了一种基于化学发光动力学方法的海水总有机碳(Total Organic Carbon,TOC)分析手段,利用臭氧与海水中有机污染物进行氧化反应进行化学发光,结合微光光电转换检测技术和对发光动力学曲线进行时间序列积分方法,实现了对海水TOC的快速、实时的现场测量。针对这个方法,进一步讨论了化学传感器、光电检测及动力学算法的设计。实验证明,该设计方法运行可靠、操作简单,为研究海洋环境提供了新的方法和思路。     

A new dry combustion method for the simultaneous determination of total organic carbon and nitrogen in seawater

A new dry combustion method for the simultaneous determination of total organic carbon and nitrogen in seawater is presented. Concentrations of total organic carbon obtained using this method average about 2.0 mg/l in surface water and 1.5 mg/l in deep water in the Northwest Atlantic. These concentrations are significantly greater than those reported using wet oxidation and wet combustion methods, but are comparable to concentrations reported by Russian workers using a similar dry combustion method. Organic nitrogen concentrations average 0.44 mg/l in surface water and 0.12 mg/l in deep water, yielding CN ratios for total organic matter of 5 and 12 respectively.     

An improved model for estimating the TOC in shale formations

Determination of the total organic carbon (TOC) from well logs is an important step in formation evaluation of shale reservoirs. The ΔlogR model is one of the most commonly used methods in determining the TOC of the source rocks. Wang et al. (2016) made three revisions on ΔlogR model to enhance the prediction accuracy, one of which is to use a changeable slope of log₁₀R_t versus porosity logs to replace a fixed value. Based on the original ΔlogR model and Wang's revision, we propose an improved model for a better TOC estimation in this paper. Specifically, the approximate linear baseline is replaced by a theoretical one. Under this condition, both the slope and resistivity and porosity log values of the baselined rocks vary from depth to depth. The determination of theoretical baseline is presented, and the varied baseline log values are obtained by a simple mathematical technique. In addition to the shale play of Western Canada Sedimentary Basin, two study areas of Sichuan Basin and Ordos Basin in China, were used to assess the applications of the proposed model and its improvement over the original model. The analysis and discussions presented in this paper indicate that the improved model offers more reliable results in shale plays with large lithological variations. Also, the TOC content of the three study areas was estimated using the proposed model. The results showed that the TOC values estimated from well logs and core analysis are in good agreement.     

Analysis of the influence that climatic variability has on the formation of the total-ozone-content field at extratropical latitudes of the Northern Hemisphere

Having applied the method of discriminant analysis to the TOMS data of satellite sounding of the total ozone content (TOC) in the March months of 1979–2008, the authors could make a new estimate of the TOC field variability in the Northern Hemisphere and interlongitudinal regularities of its changes under the action of climatic variability. The effects of temperature variations in the polar stratosphere, El Niño, and quasi-biennial oscillation (QBO) have proven comparable and reach 80 DU in some regions. The influence of the Arctic Oscillation (AO) reaches 40 DU. The regions of TOC variations and their location and dimensions change depending on the phases of QBO, AO, and El Niño-Southern Oscillation (ENSO). Three regions of increased TOC—over Europe, Eastern Siberia, and the Pacific Ocean—are formed in years with a warm stratosphere. A compensating TOC decrease takes place in the tropics and over Greenland. In the years of El Niño and the easterly QBO phase, the TOC increases over Europe and drops over the central Pacific, as well as to the south from 45° N. The AO controls the ozone growth over most of Eurasia at temperate latitudes and its weak drop over the Atlantic. It was impossible to obtain such quantitative estimates with the use of methods based on an independent analysis of the TOC series at individual points of the coordinate grid. Testing with the Monte Carlo method confirmed that the results obtained are significant with a probability of 95–99.9%.     

Ground-based measurements of total ozone content by the infrared method

To interpret the ground-based measurements of the spectra of direct solar infrared radiation with the help of a Brucker Fourier-spectrometer, a technique for determining the total ozone content (TOC) was developed and implemented. The TOC was determined using six spectral intervals of an ozone-absorption band of 9.6 μm and the shortwave panel of a carbon-dioxide-absorption band of 15 μm, where the impact of other atmospheric parameters on the measured solar radiation was reduced to a minimum. The potential errors of the infrared method for determining the TOC for the chosen spectral scheme with the influence of measurement errors and vertical profiles of temperature are less than 1% for different signal-to-noise ratios and zenith angles of the sun. We analyzed 269 high-resolution (0.005–0.008 cm^?1) spectra of solar infrared radiation measured in Peterhof over 52 days from March to November, 2009. The resulting values of TOC were compared with the results of independent ground-based TOC measurements in Voeikovo (Main Geophysical Observatory) using a Dobson spectrophotometer and an M-124 ozonometer, as well as with the Ozone Monitoring Instrument (OMI) satellite data. The mean errors between the results of TOC measurements with the help of the three ground-based probes constitute no more than 0.4%. The rms errors between data obtained by the Brucker spectrometer and the given satellite and ground-based probes constitute 3–4%. A comparison between different series of measurements indicated that the upper estimate for the error of TOC measurements by the Brucker spectrometer was 2.5–3% (when the possible spatial and temporal errors in measurements are disregarded). An analysis of the diurnal variations in the TOC measurements for stable atmospheric conditions yields an upper estimate of ～3 DU (around 1%) for the random component of error in TOC measurements by the Brucker spectrometer.     

电活化硫酸盐处理四环素类废水的研究

本文构建以掺硼金刚石(Boron-doped diamond,BDD)为阳极、不锈钢为阴极、硫酸盐为电解质的电化学体系,考察了电流密度、pH值、硫酸盐浓度以及初始四环素浓度等四个因素对电化学氧化降解废水中四环素的影响,运用响应曲面法对运行参数进行优化;通过电子自旋共振检测技术分析电化学反应中产生的自由基,探究了间歇通电模式下电化学体系持续氧化机理。结果表明,四个因素对TOC去除率的影响大小次序为:电流密度>初始四环素浓度>初始pH值>硫酸盐浓度,其中初始pH值和硫酸盐浓度与电流密度和初始四环素浓度的交互作用对TOC去除率的影响较为显著;最佳运行参数为pH值为5,电流密度为100 mA·cm^-2,硫酸盐浓度为0.25 mol·L^-1,初始四环素浓度为1000 mg·L^-1;间歇通电模式下,BDD电极表面产生的SO₄^·-等高活性物质间相互转化提供了体系的可持续氧化能力。该研究结果为电化学氧化技术的实际应用提供了节省能耗的有效途径。     

Seismic based characterization of total organic content from the marine Sembar shale,Lower Indus Basin,Pakistan

The exploration and production of unconventional resources has increased significantly over the past few years around the globe to fulfill growing energy demands. Hydrocarbon potential of these unconventional petroleum systems depends on the presence of significant organic matter; their thermal maturity and the quality of present hydrocarbons i.e. gas or oil shale. In this work, we present a workflow for estimating Total Organic Content (TOC) from seismic reflection data. To achieve the objective of this study, we have chosen a classic potential candidate for exploration of unconventional reserves, the shale of the Sembar Formation, Lower Indus Basin, Pakistan. Our method includes the estimation of TOC from the well data using the Passey’s ΔlogR and Schwarzkofp’s methods. From seismic data, maps of Relative Acoustic Impedance (RAI) are extracted at maximum and minimum TOC zones within the Sembar Formation. A geostatistical trend with good correlation coefficient (R²) for cross-plots between TOC and RAI at well locations is used for estimation of seismic based TOC at the reservoir scale. Our results suggest a good calibration of TOC values from seismic at well locations. The estimated TOC values range from 1 to 4% showing that the shale of the Sembar Formation lies in the range of good to excellent unconventional oil/gas play within the context of TOC. This methodology of source rock evaluation provides a spatial distribution of TOC at the reservoir scale as compared to the conventional distribution generated from samples collected over sparse wells. The approach presented in this work has wider applications for source rock evaluation in other similar petroliferous basins worldwide.     

辽河口芦苇湿地土壤有机碳的积累特征研究

通过研究辽河口芦苇湿地土壤有机碳、石油类、阴离子表面活性剂(LAS)、多环芳烃(PAHs)及脂肪酸的垂直分布特征,探讨了不同来源有机物在芦苇湿地的埋藏和降解规律.土壤样品采集于2009年3月,研究发现,有机碳含量范围为0.3％～9.3％,石油烃含量范围为19.04～482.31mg/kg(干重)之间,LAS含量范围为0.84～19.28mg/kg(干重),PAHs含量范围为2.59～4.40 mg/kg(干重).总脂肪酸含量范围为5.72～190.69mg/kg(干重).表层有机碳含量丰富,来源广泛.辽河油田不同年代的采油环保措施可能是芦苇湿地土壤中石油类聚集量多寡的主要因素,芦苇根际的调控调节作用和微生物的选择性降解也对土壤石油类化合物分布起到重要作用.LAS含量从土壤表层向下迅速降低了67.0％,是所研究有机物中降解最迅速的一种.PAHs自表层至底层没有明显的变化趋势.细菌是辽河芦苇湿地土壤有机碳再生产的主要承担者,在次表层以下,细菌生产所利用的有机碳主要来自现场的生产.     

渤海表层沉积物中有机碳的分布和来源

大河影响下的陆架边缘海沉积有机碳的分布和来源是全球碳循环研究的重要内容。本研究于2012年5月采集了渤海海域的29个表层沉积物样品,分析了粒度组成、总有机碳(TOC)、总氮(TN)、木质素含量和稳定碳同位素丰度(δ13C)等参数,结合基于蒙特卡洛模拟的三端元混合模型,定量研究了沉积物中有机碳的分布和来源情况,并讨论了其影响因素。结果表明,研究区域表层沉积物中TOC含量为0.19%~0.81%,渤海中部泥质区站位(大于0.65%)明显高于其周围砂质区域站位(小于0.40%);TOC与黏土含量也有显著的正相关性,说明细颗粒沉积物容易富集有机碳。沉积有机碳的δ13C范围为-23.7‰~-21.8‰,显示沉积有机碳是海源和陆源有机碳的混合输入。木质素参数,如C/V、S/V和LPVI的数值范围显示研究区域表层沉积物中木质素主要来源于被子植物草本组织与木本组织的混合,同时有少量裸子植物的贡献。基于蒙特卡洛模拟的三端元混合模型显示研究区域沉积物中有机碳主要来源于海洋浮游植物,平均为64%,陆源有机碳中来自土壤的贡献最高(平均为27%),C₃维管植物的贡献较少(平均为9%)。海洋浮游植物有机碳主要分布在渤海中部泥质区及离岸较远的区域,而土壤有机碳和C₃维管植物有机碳则主要沉积在河口附近及近岸区,并可以离岸输运到较远的地方。     

Determination of the total ozone content from data of satellite IR Fourier-spectrometer

Examples of retrieval of the total ozone content (TOC) from the spectra of outgoing thermal radiation measured by the IRFS-2 device on the Meteor-M no. 2 meteorological satellite are presented. The technique, developed by the authors and based on an artificial neural network (ANN) approach with the use of TOC measurements by the satellite OMI device, is applied. A comparison of the results with the data of independent TOC measurements has shown their agreement within 2–5% for global ensemble and within 3–6% for separate latitudes and seasons. The errors estimated for IRFS-2 TOC measurements are close to the errors in measurements by a similar IASI device from the MetOp (EUMETSAT) satellite.     

Effects of the equatorial quasi-biennial oscillation in the total ozone content over Russia

On the basis of ground-based measurements of total ozone content (TOC) over Russia and a number of neighboring states during 1973–2002, the amplitudes and phases of TOC variations caused by the quasi-biennial oscillation (QBO) of wind in the equatorial stratosphere are estimated for different regions and for the whole area. The seasonal dependence of the QBO effect in the TOC is analyzed. It is shown that the magnitude and even the sign of the effect depend on the relation between the equatorial QBO phase and the season. The regional empirical models of seasonally dependent QBO effects are constructed. It is found that the seasonal dependence of regional effects accounts for 4% (in the north of the area) to 20% (in the south) of the interannual variability of the TOC. The relation between the QBO effect and the 11-year cycle of solar activity is analyzed. Significant differences are revealed in the effects under the conditions of maximum and minimum solar activity. The QBO effects obtained from observations at Russian stations, satellite measurements with a TOMS instrument, and spectrometric observations of the TOC at western European stations are compared, and their satisfactory agreement is shown. An analysis of the results suggests that the QBO effects in the TOC over Russia are caused by several interacting factors and apparently reflect their regional properties.     

浮体自由衰减运动阻尼识别方法误差分析

讨论了使用Froude法和Faltinsen法识别线性和非线性阻尼系数时的系统误差。通过回顾两种方法的推导过程,论证了方法的内在假设,并量化两种方法的系统误差。为减少识别过程误差,文中提出了直接积分法,并依据数值与试验数据,讨论了3种识别方法识别结果。结果表明,Froude法相比于Faltinsen法能更好地预报线性和非线性阻尼系数。对于低阻尼浮体问题,Froude法和Faltinsen法可以给出相对准确的预测,而对于强阻尼浮体问题,Froude法与Faltinsen法在确定的线性和非线性阻尼系数中会给出大于5%的系统误差,而直接积分法展示了较高的识别精度。     

XRF岩心扫描估算海洋沉积物有机碳含量的适用性

X射线荧光光谱仪(XRF)的沉积物岩芯扫描技术可以无损、快速获得高分辨率的溴(Br)计数信息, 可用来估算海洋沉积物中有机碳含量, 但是其准确性及各种校正方法的效果还需要深入研究。文章选择两根在有机质来源构成上有明显差异的阿拉伯海和南海的沉积柱, 系统开展了沉积物有机碳(total organic carbon, TOC)含量与Br计数的相关性分析, 深入剖析了沉积物含水量、Br计数校正方法等对利用Br计数估算沉积物TOC含量的影响及评估该方法的适用性。对于有机质含量较高的海洋沉积物而言, Br计数与TOC含量之间存在较好的相关性, 且其相关性与是否校正Br计数没有显著关系。在陆源有机质输入量比较大的沉积物样品中, 则需谨慎采用Br计数来估算沉积物的总有机碳含量。     

Spatial Distribution of Polychlorinated Biphenyls （PCBs） Contaminants in the Tidal-flat Sediments of Yangtze Estuary

1 IntroductionYangtze River estuary is the biggest one in China, and there are domestic and manufactural rubbish disposal sites for Shanghai city in this tidal-flat. The Shanghai city, the whole Yangtze delta, or even all the Yangtze basin, will be PCBs contaminant sources of Yangtze estuary tidal-flat[1]. According to literatures so far, only two investigations for waters have included PCBs in the Yangtze estuary[2, 3]. No PCBs pollution of the tidal-flat sediments has been reported…     

Total organic carbon distribution and budget through the Strait of Gibraltar in April 1998

In order to investigate total organic carbon (TOC) exchange through the Strait of Gibraltar, samples were taken along two sections from the western (Gulf of Cádiz) and eastern (Western Alboran Sea) entrances of the Strait and at the middle of the Strait in April 1998. TOC was measured by using a high-temperature catalytic oxidation method. The results referenced here are based on a three-layer model of water mass exchange through the Strait, which includes the Atlantic inflow, Mediterranean outflow and an interface layer in between. All layers were characterised by a decrease of TOC concentrations from the Gulf of Cádiz to the Western Alboran Sea: from 60–79 to 59–66 μM C in the Atlantic inflow and from 40–60 to 38–52 μM C in the Mediterranean waters, respectively. TOC concentrations in the modified North Atlantic Central Water varied from 43 to 55 μM C. Intermediate TOC values were measured in the interface layer (43–60 μM C). TOC concentrations increased from the middle of the Strait towards continents indicating a contribution of organic carbon of photosynthetic origin along Spain and Morocco coasts or TOC accumulation due to upwelling in the northeastern part of the Strait. Our results indicate that the short-term variability caused by the tide greatly impacts the TOC distribution, particularly in the Gulf of Cádiz. The TOC input from the Atlantic Ocean to the Mediterranean Sea through the Strait of Gibraltar varies from 0.9×10⁴ to 1.0×10⁴ mol C s⁻¹ (or 0.28×10¹² to 0.35×10¹² mol C year⁻¹, respectively). This estimate suggests that the TOC inflow and outflow through the Strait of Gibraltar are two and three orders of magnitude higher than reported via the Turkish Straits and Mediterranean River inputs.     

高原泥炭记录揭示的全新世季风快速变化

利用青藏高原东北缘的泥炭沉积记录,重建了该地区全新世冬、夏季风快速波动历史,清晰地识别出9次可与北大西洋浮冰碎屑事件及低纬海面降温事件相对比的气候干冷事件。总有机碳含量频谱分析揭示的1 428、512、2552、17 a气候准周期,表明中纬度地区百年至千年尺度气候韵律的存在,全新世气候快速变化具有全球性。     

Temporal Variability of Total Ozone in the Asian Region Inferred from Ground-Based and Satellite Measurement Data

This paper reports investigation data on the temporal variability of total ozone content (TOC) in the Central Asian and Tibet Plateau mountain regions obtained by conventional methods, as well as by spectral, cross-wavelet, and composite analyses. The data of ground-based observation stations located at Huang He, Kunming, and Lake Issyk-Kul, along with the satellite data obtained at SBUV/SBUV2 (SBUV merged total and profile ozone data, Version 8.6) for 1980–2013 and OMI (Ozone Monitoring Instrument) and TOU (Total Ozone Unit) for 2009–2013 have been used. The average relative deviation from the SBUV/SBUV2 data is less than 1% in Kunming and Issyk-Kul for the period of 1980–2013, while the Huang He Station is characterized by an excess of the satellite data over the ground-based information at an average deviation of 2%. According to the Fourier analysis results, the distribution of amplitudes and the periods of TOC oscillations within a range of over 14 months is similar for all series analyzed. Meanwhile, according to the cross-wavelet and composite analyses results, the phase relationships between the series may considerably differ, especially in the periods of 5–7 years. The phase of quasi-decennial oscillations in the Kunming Station is close to the 11-year oscillations of the solar cycle, while in the Huang He and Issyk-Kul stations the TOC variations go ahead of the solar cycle.     

Calibration of the mudrock compaction curve by eliminating the effect of organic matter in organic-rich shales: Application to the southern Ordos Basin,China

The mudrock log-derived compaction curve is a significant tool for investigating the primary migration of hydrocarbon, predicting fluid overpressure, estimating formation erosion thicknesses and restoring the buried history and paleo-structure of a basin. However, the presence of kerogen in organic-rich shales can create typically high logging values of the acoustic transit time. Thus, the abnormally high values of the acoustic transit time for organic-rich rocks may not truly reflect the porosity variations of subsurface rocks, leading to great uncertainties in the understanding of the mudstone compaction and a certain amount of error in the abnormal fluid pressure estimation when using the mudrock log-derived compaction curve. Therefore, it is necessary to recalibrate the mudstone compaction curve by eliminating the increment of the acoustic transit time caused by the kerogen content of organic-rich mudstones. Taking the southwest Ordos Basin as an example, this paper presents a new equivalent volume model based on the composition of organic-rich shale in which the kerogen content is also considered. Based on the quantitative relationship between the rock composition and the acoustic transit time, a quantitative formula for calculating the acoustic transit time increment caused by the kerogen is derived. This formula shows that the increment depends not only on the organic content but also on the occurrence state, pore size, pore fluid composition and other factors. X-ray diffraction (XRD) data were used to determine the main mineral composition of the mudstone and to calculate the acoustic transit time of the rock skeleton. Then, the mudstone compaction curve in the Zhenjing area was calibrated by combining the measured porosity and total organic carbon (TOC) of the mudstone based on the correction formula. The compaction characteristics varied significantly between before and after the calibration. The slope of the normal compaction trend (NCT) line decreased by 30–55%, and the acoustic transit time deviation from the NCT in the undercompaction interval decreased significantly. The overpressure at the maximum burial depth estimated by the equivalent depth method is in better agreement with the results obtained by numerical simulation after the calibration, and the porosity determined from the well log after the calibration is also closer to the true measured value. The method proposed in this paper is of great significance for improving the reliability and accuracy of compaction research on organic-rich mudstones, especially for the accurate estimation of abnormal pressure in the source rock layer. Additionally, it can be used as an effective reference for mudstone compaction studies in similar geological settings areas or basins.