Determination of hydrocarbon distributions in oils and sediment extracts by gas chromatography—high resolution mass spectrometry

The distributions of steroid and triterpenoid hydrocarbons in crude oils and sedimentary rock extracts can be routinely determined by the direct injection of the sample into a gas chromatograph coupled to a mass spectrometer (GC-MS). The mass spectrometer is operated at a resolution of about 2500 (10% valley), and only the ion intensities at selected accurate mass values, diagnostic of the structural types of interest, are monitored throughout the analysis. The distributions, so obtained, find application in the assessment of the source and thermal maturity of crude oil accumulations in the subsurface. This technique eliminates chromatographic separation steps and combines two analyses in one. Thus, more geological samples and reference mixtures may be analyzed in a given time.     

Application of two new LC–ESI–MS methods for improved detection of intact polar lipids (IPLs) in environmental samples

Intact polar lipid distributions have become a valuable tool for the study of microbial ecosystems. In order to expand the detection and interpretation of the presence of these lipids, improved analytical methods are needed. Therefore, two high pressure liquid chromatography–electrospray ionization tandem mass spectrometry (HPLC–ESI–MS²) methods, based on hydrophilic interaction chromatography (HILIC) and reversed phase (RP) chromatography were developed, taking advantage of new chromatographic possibilities such as smaller particle size and recently developed column packing material. Both were optimized to cover the broad range of compounds found in environmental samples and to cope with the associated complex sample matrices. The capabilities of the methods were tested on pure standards and an environmental sample. Both methods offer improved peak resolution and detection limit, and reduced chromatographic background at twofold shorter run time compared with the previous method based on a diol column. The HILIC method offers separation according to lipid class similar to a diol column, so can be recommended for lipid fingerprinting. The method based on RP separation offers the unique possibility of analyzing intact polar lipids and core lipids in the same chromatographic run and an alternative mode of lipid separation based mainly on side chain structure. The method is especially suitable for separation of compounds based on side chain length, degree of saturation and/or presence of acyl/ether bonds. The combination of both newly developed chromatographic methods provides a powerful tool for the analysis of lipid distributions in environmental samples at ultra-low concentration.     

The determination of biomarker distributions by tandem mass spectrometry

The rapid development of biomarker geochemistry and its application to petroleum exploration problems has been due in no small part to gas chromatography-mass spectrometry (GC-MS). The recent availability of hybrid and triple stage quadrupole mass spectrometers have introduced a number of novel ways for the detection and identification of biomarkers present in extremely complex mixtures of organic compounds from various sources including crude oils and source rock extracts.A triple stage quadrupole mass spectrometer has been used in the MS/MS mode with both a gas chromatograph and direct insertion probe as inlet systems, to develop alternative methods for biomarker analyses. Selected ions formed in the ion source of the mass spectrometer are permitted to enter the collision cell where, following collision with an inert gas, the daughter ions are separated using the third quadrupole. In this manner specific parent/daughter ion relationships are utilized to monitor and resolve classes of biomarkers or individual components from within a complex mixture. Furthermore, deuterated analogues of naturally occurring biomarkers can be utilized for quantitation purposes since the parent/daughter relationship for the standard will differ, depending on the number of deuterium atoms present, even though the relative retention times are identical.The ability of MS/MS to resolve components spectrometrically as well as chromatographically greatly enhances the analytical short-column capabilities of this system. In this paper the utilization of GC-MS/MS and the direct insertion probe MS/MS to determine biomarker distributions in crude oils both qualitatively and quantitatively are discussed. The results from the study show that it is possible to use the probe data to rapidly correlate oils on the basis of their source materials and if necessary select samples for more detailed analysis by GC-MS/MS. A major advantage of the direct insertion probe method is speed of analysis although some component resolution is lost. In an effort to minimize this problem and still maintain the rapid analysis time, the use of short columns in the GC is also described. This approach provides the ability to undertake relatively rapid analyses with limited chromatographic resolution but at relatively high levels of sensitivity.     

应用小波变换与二维分形技术预测奥灰裂隙发育带

以许厂煤矿的应用为例，介绍了小波变换和二维分形技术的基本理论以及预测奥灰裂隙发育带的方法、步骤及效果。理论与实际分析表明，在预测奥灰裂隙发育带中，小波变换可以提高地震资料的分辨率和信噪比，二维分形参数有很高的参考价值，二者的结合为预测奥灰裂隙发育提供了一种有效的方法。     

High Resolution Stepped-Combustion Mass Spectrometry: Application to the Detection and Analysis of Fine-Grained Diamond in Meteorites and Rocks

An analytical system and operating protocol are described for high resolution, stepped-combustion mass spectrometry, designed for the extraction, purification, quantification and isotopic analysis of light elements (e.g. C and N) in fine-grained reduced components (e.g. diamond) which have been chemically extracted from natural samples (e.g. meteorites). Specifically, a simple model has been developed for the extraction of diamond from meteorite and its analysis by high resolution stepped heating under an atmosphere of oxygen. Changes in the pressure of oxygen within the range 1.3 to 12kPa (10 to 90 torr) were not found to have any detectable effect on the combustion. Results obtained by this procedure were compared with those predicted by a model and excellent agreement was found, taking into account the limitations of this approach. Results of a preliminary attempt to find fine-grained diamond in a lamproite are outlined.     

Improved Background Correction in the Analysis Of Cadmium by Flame Atomic Absorption

Cadmium signals obtained by direct aspiration of highly concentrated solutions of rocks and other geochemical samples are swamped by strong matrix background signals. Mainly because of iron interference, the deuterium source or other continua are not satisfactory for background correction. In order to isolate atomic absorption by cadmium the total signal and the background signal have to be measured precisely. Sequential measurements in the double beam mode with electrodeless discharge lamps of cadmium and arsenic at 228.80 and 228.81 nm produced a set of uninterfered data for cadmium within marginally useful detection limits of (0.10 ppm in granite, 0.16 ppm Cd in limestone). Simple extraction of the sample powders with nitric acid dissolves only part of the sample matrix but most of the cadmium. In this way higher relative and absolute cadmium concentrations in solution and better detection limits are obtained (e.g. 0.02 ppm Cd in granite). This approach allows cadmium in geosamples at levels below 0.3 ppm to be determined more accurately than via hydrofluoric acid dissolution.     

高分辨率城市活断层地震资料处理技术

高分辨率地震方法在城市活断层探测中,已成为一种不可缺少的方法技术。在活断层探测中,地震方法不但能确定断层的产状,而且还能确定断层的上断点。由于大多数地震资料都是在干扰背景较强的情况下取得的,高分辨率城市活断层中,地震资料处理的关键是在不降低地震记录分辨率的前提下,提高地震记录的信噪比。一般来说,提高地震记录的分辨率和信噪比是相互矛盾的。如何解决这一对矛盾,这里结合目前正在开展的城市活断层探测课题,进行了比较深入的研究,并取得了较好的处理效果。     

Statistical radio astronomy of the 21st century

The exponential development of radio-astronomy methods (sensitivity, resolution, depth of surveys, etc) has led to the need for new methods aimed at distinguishing weak signals in the midst of numerous background signals, as has long been the case for radio astronomy at meter wavelengths. Centimeter-wavelength data accumulated with existing radio telescopes (such as the RATAN-600 reflector—the largest radio telescope in Russia) are presented, and expected problems for major new radio telescopes of the 21st century, such as the Square Kilometer Array, are discussed. The effectiveness of using certain tested methods to derive astrophysically important results through reasonable statistical processing of large datasets is shown. In experiments conducted with RATAN-600, these methods lead to an enhancement in sensitivity by an order of magnitude compared with the sensitivity of a resolving element.     

岩土层含水量分层监测系统的研究及应用

开发为地质灾害预测预报所需用的岩土层含水量和渗透力测试仪,并和气候雨量、地质灾害成灾规律联系起来,是我国地质灾害监测预报发展的趋势。岩土层含水量分层监测系统是采用TDR（Time Domain Refiectometry）技术原理、方法研制的仪器,通过波导棒探针发射的电磁波射入岩土层,测量电磁波脉冲从波导棒的起点传播到接收末端的反射电压值,此反射电压值与岩土体本身含水量介电常数有函数关系,经过计算转换为测点岩土体积含水量,实时测量和采集地质灾害岩土层含水量和渗透力参数。介绍了该监测系统的基本原理、主要技术参数、监测工艺技术方法以及现场应用情况。     

CO2-Laser Extraction-Static Mass Spectrometry Analysis of Ultra-Low Concentrations of Nitrogen in Silicates

A new installation for the analysis of picomole quantities of nitrogen has been designed and constructed. It permits the simultaneous analysis of N and rare gases extracted from silicates by heating. The extraction procedure involves the use of a CO₂ laser as a heater, and the analysis is made by static mass spectrometry using a high sensitivity, high resolution mass spectrometer. Procedural blanks of 2 picomoles N₂ (60 picogram N) allow us to analyse routinely N in mg-sized samples such as mantle-derived and meteoritic minerals, and Lunar soil grains.     

Seismological study of the central Ecuadorian margin: Evidence of upper plate deformation

A seismic study of a segment of the convergent margin of Ecuador is presented. During the SISTEUR campaign a network of 24 Ocean Bottom Seismometers (OBS) was deployed on the Carnegie Ridge, one line along the main axes of the ridge and two lines across the strike of the edge of the ridge, during one month. This marine network was complemented with a land network of 20 stations distributed in two lines: one parallel to the margin and the other perpendicular to it.The seismic event recorded by these networks, were located using different crustal models defined from the wide-angle seismic data modeling. Relative location techniques were used to improve earthquake locations. Seismogram waveform modeling allowed us to constrain hypocentral location for events farther than ～50 km from the network. This modeling also provided additional information to constrain the focal mechanisms of these events. The upper limit of the Interplate Seismogenic Zone (ISZ) is estimated to be at a 10 km depth in the region. The background seismic activity of the upper plate provided new insights:1) A seismic cluster that reaches the base of the overriding plate is linked to the Jipijapa-Portoviejo fault. The reactivation of this Quaternary fault is confirmed by focal mechanisms that provide rupture planes parallel to its superficial projection (N10°–N25°).2) The focal mechanisms presented in this study are compatible with a homogeneous regional stress field corresponding to an E–W to ESE–WNW compression and an NNE–SSW extension. The presence of strike-slip deformation, with a reverse component, corresponds to the NNE escape of the North Andean Block. Normal faulting accommodating this movement suggests that this part of the North Andean Block cannot be considered as a rigid block.     

<Emphasis Type="Italic">Nummulites solitarius — Nummulites burdigalensis</Emphasis> lineage in Kutch with remarks on the age of Naredi Formation

Three successive subspecies of Nummulites burdigalensis evolved from N. solitarius. These include N. burdigalensis keupperi, N. burdigalensis burdigalensis and N. burdigalensis cantabricus. The evolving lineage is traced in a borehole drilled through the Naredi Formation of Kutch. The associated taxa include N. solitarius and N. fraasi in the lower part and Assilina laxispira and A. spinosa in the upper part of the formation. The better stratigraphic resolution achieved by subspecies identification and the lately redefined Ilerdien Stage in the background of Early Eocene carbon isotope excursion marker, lead to constrain the age of Naredi Formation as Early Eocene, ranging from shallow-benthic zones SBZ6 to SBZ11.     

Origin of Hydrocarbons in Hydrothermal Sulfide Ores in the Mid-Atlantic Ridge

The Rainbow hydrothermal field (36° N Mid-Atlantic Ridge) is one of the three presently known fields related to serpentinization of ultramafic rocks accompanied by the formation of hydrogen- and methane-rich solutions. Gas chromatographic (GC) and molecular gas chromatographic–mass spectrometric (GC-MS) investigations of sulfide ores and sediments from this field confirmed a predominantly biological nature of bitumoids related to the high-temperature transformation of biomass of the hydrothermal biological community. At the same time, ores of the Rainbow field contain significant amounts of compounds that are not directly related to biogenic synthesis. This fact suggests the possibility of an abiogenic synthesis of methane and even complex hydrocarbons during the serpentinization of ultramafic rocks.     

Conceptual Numerical Modeling of Large-Scale Footwall Behavior at the Kiirunavaara Mine,and Implications for Deformation Monitoring

Over the last 30 years, the Kiirunavaara mine has experienced a slow but progressive fracturing and movement in the footwall rock mass, which is directly related to the sublevel caving (SLC) method utilized by Luossavaara-Kiirunavaara Aktiebolag (LKAB). As part of an ongoing work, this paper focuses on describing and explaining a likely evolution path of large-scale fracturing in the Kiirunavaara footwall. The trace of this fracturing was based on a series of damage mapping campaigns carried out over the last 2 years, accompanied by numerical modeling. Data collected from the damage mapping between mine levels 320 and 907 m was used to create a 3D surface representing a conceptual boundary for the extent of the damaged volume. The extent boundary surface was used as the basis for calibrating conceptual numerical models created in UDEC. The mapping data, in combination with the numerical models, indicated a plausible evolution path of the footwall fracturing that was subsequently described. Between levels 320 and 740 m, the extent of fracturing into the footwall appears to be controlled by natural pre-existing discontinuities, while below 740 m, there are indications of a curved shear or step-path failure. The step-path is hypothesized to be activated by rock mass heave into the SLC zone above the current extraction level. Above the 320 m level, the fracturing seems to intersect a subvertical structure that daylights in the old open pit slope. Identification of these probable damage mechanisms was an important step in order to determine the requirements for a monitoring system for tracking footwall damage. This paper describes the background work for the design of the system currently being installed.     

北淮阳东段塘湾岩体地球化学特征、锆石U-Pb测年及地质意义

位于安徽北淮阳东段的塘湾岩体为凌家冲杂岩体的重要组成部分,岩石类型为石英闪长岩。该岩体偏铝质、低硅、富碱、高钠,属于高钾钙碱性系列岩石;稀土元素含量中等,（La/Yb）N与HREE/LREE值较高,重稀土相对亏损,Eu弱负异常,属轻稀土富集型;大离子亲石元素Rb、Ba、K、La、Nd富集,高场强元素Nb、Ta、Ti、P亏损。LA-ICP-MS锆石U-Pb测年结果显示塘湾岩体206Pb/238U年龄为（138.0±2.9）Ma,表明岩体为早白垩世岩浆活动的产物。基于区域地质背景及构造环境判别,塘湾石英闪长岩形成于后碰撞伸展构造环境。     

Subglacial bedform geomorphology of the Irish Ice Sheet reveals major configuration changes during growth and decay

The belated realisation that ribbed (Rogen) moraines form such an integral part of Irish geomorphology, and the piecemeal approach to previous drumlin mapping, is probably responsible for the highly contrasting views of palaeoflow patterns of the Irish Ice Sheet. Using a high resolution (25 m) digital elevation model we present morphological maps of a large part (100 × 100 km) of the so‐called ‘Drumlin Belt’ of north central Ireland. The landforms comprise mostly ribbed moraine much larger than found elsewhere (up to 16 km in length), which in places are superimposed on each other. Contrary to most prior assessments we find the bedform record to contain numerous and overlapping episodes of bed formation (ribbed moraine, drumlins and crag‐and‐tails) that provide a palimpsest record of changing flow geometries. These demonstrate an ice sheet with a centre of mass and flow geometry that changed during growth and decay. Using distinctive flow patterns and relative age relationships between them we reconstruct ice sheet evolution into four phases during a single glacial cycle. In phase 1 (early in the glacial cycle), Scottish and local ice coalesced to form a northeast‐centred Irish Ice Sheet. As it grew its centre of mass migrated southwards, culminating in a major N–S divide positioned down the east of Ireland (phase 2, ca. Last Glacial Maximum). During retreat, the centre of mass migrated at least 120 km northwards and became established in northwest Ireland and at this point a dramatic bedforming event produced one of the world's largest and most contiguous ribbed moraine fields (phase 3). Final deglaciation is thought to be by fragmentation into many topographically controlled minor ice‐caps (phase 4). Rather than any dramatic or unexpected behaviour, the reconstructed phases indicate a relatively predictable pattern of ice sheet growth and decay with changes in centres of mass, and does not require major readvances or ice‐stream events. Copyright © 2001 John Wiley & Sons, Ltd.     

Evaluating the anthropogenic impacts on groundwaters; a methodology based on the determination of natural background levels and threshold values

The present work investigates the long-term effects of human intervention on groundwaters based on the determination of natural background levels (NBLs) and threshold values (TVs) for groundwater electrical conductivity, chloride, ammonium, sulphates and nitrates. The methodology adopted is the one proposed in the 6th Framework European Project ??BRIDGE??, which was applied with some adjustments in Rhodope area (Northern Greece). The study area was especially selected because it incorporates two distinct subareas: the northern one which can be safely considered as a pristine area, where NBLs for groundwaters were assessed from; the southern part which forms a typical Mediterranean region, intensively cultivated for the last 40?years. Groundwater TVs were determined considering two types of groundwater receptors: (a) groundwater ??itself?? and (b) groundwater dependent lagoons in the coastal part of the study area. Results showed that groundwater quality is altered seriously from its natural background composition indicating how human activities have affected groundwater quality and showed that chemical status of groundwater has been seriously aggravated. The number and the spatial distribution of monitoring locations exceeding TVs revealed that chloride and nitrates are the most serious threats for groundwater in the study area.     

Alkyl amides in two organic-rich anoxic sediments: A possible new abiotic route for N sequestration

Fixed nitrogen (N) plays an integral role in global cycling; while most is recycled to refuel primary productivity, a small fraction escapes to be preserved and stabilised in sediments. Despite decades of research, the functionality and reactivity of this sequestered organic N has been poorly understood. This study was undertaken to shed light on this problem by characterising the bulk sediment organic matter using nuclear magnetic resonance (NMR), followed by molecular level analysis using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). We studied two organic-rich anaerobic sediments, one from a freshwater system and another from a marine paralic basin. Mangrove Lake, Bermuda (marine) and Mud Lake, Florida (freshwater) have been shown in past studies to contain high levels of N-containing organic matter. Our resulting multidimensional NMR data suggests the existence of a new type of amide functionality in both these lake sediments, and we investigated this further using FT-ICR-MS and gas chromatography mass spectrometry (GC-MS). FT-ICR-MS confirmed the existence of homologous series of CHNO containing compounds, whose structures are verified using GC-MS as alkyl amides. Model reactions involving naturally occurring esters and ammonia suggest the source of alkyl amides to be amidation of esters with sedimentary ammonia derived from anaerobic degradation of organic matter. This expands upon previous hypotheses for preservation of amide containing compounds that call upon biological/abiological protection of proteins and peptides or the formation of refractory nitrogenous adducts.     

Seismic random noise attenuation using artificial neural network and wavelet packet analysis

In this paper, we present a method for attenuating background random noise and enhancing resolution of seismic data, which takes advantage of semi-automatic training of feed forward back propagation (FFBP) artificial neural network (ANN) in a multiscale domain obtained from wavelet packet analysis (WPA). The images of approximations and details of the input seismic sections are calculated and utilized to train neural network to model coherent events by an automatic algorithm. After the modeling of coherent events, the remainder data are assumed to be related to background random noise. The proposed method is applied on both synthetic and real seismic data. The results are compared with that of the adaptive Wiener filter (AWF) in synthetic shot gather and real common midpoint gather and also with that of band-pass filtering on real common offset gather. The comparison indicates substantially higher efficiency of the proposed method in attenuating random noise and enhancing seismic signals.