Total Organic Carbon Measurements Research Articles

Quantitative Characterization and Determination of the Main Factors That Control Fracture Development in the Lower Paleozoic Shale in Southeastern Chongqing, China

The Longmaxi and Niutitang Formations are typical shale reservoirs in southeastern Chongqing. Since the Paleozoic, southeastern Chongqing has experienced multistage tectonic movement and diagenesis, resulting in the formation of a large number of natural fractures. In shale reservoirs, fractures not only provide seepage channels for oil and gas migration but also play an important role in the oil and gas reservoir space. Natural fractures provide a flow path from source rock to reservoir during oil filling and connect hydraulic fractures, matrix pores, and boreholes during production. Therefore, identifying the main factors that control the development of natural fractures in the Longmaxi and Niutitang Formations in southeastern Chongqing has a guiding significance for the efficient development of shale reservoirs in this area. By considering the Longmaxi and Niutitang Formation shales as case studies, using field outcrops, drilling cores, and other data, and conducting X-ray diffraction (XRD) analysis as well as total organic carbon (TOC) measurements, the quantitative parameter characteristics and main factors that control the development of natural fractures in reservoir shales were examined in detail. The results obtained showed that there are three types of fractures in the lower Paleozoic shale in southeastern Chongqing, which are structural, diagenetic, and abnormal high-pressure fractures. Among them, the fractures in the Longmaxi Formation shale, which are relatively abundant, predominantly consist of low-angle and high-angle inclined fractures, while the Niutitang Formation predominantly consists of high-angle fractures. Additionally, the investigation of fracture size and fracture density, as well as correlation analyses, showed that the fractures of the Lower Paleozoic shale are predominantly micro fractures that play a key role in improving reservoir seepage. It was also noted that the development of fractures is affected by several factors, including tectonic stress, mineral composition, organic carbon content, and rock thickness. The degree of fracture development was found to be positively correlated with brittle mineral and quartz contents, and high organic matter contents also significantly favored the formation micro fractures.

Heavy Metal Content and Physico-Chemical Analyses of Soils under the Litter of some Medicinal Taxa in the Luki Biosphere Reserve, Democratic Republic of the Congo

Aim: The aim of this study was to compare the texture, mineral element and heavy metal content of the soil under the litter of different selected species in relation to the plan of their pedogenesis.
 Methods: The granulometric analysis of the various samples based on laser diffraction, measurements of Total Nitrogen and Total Organic Carbon were performed using the Elemental Analyzer, the Organic Matter content is estimated by the loss of ignition method using a Salvis furnace, In order to estimate the CaCO3 content. The same samples were heated in the oven at 1000°C for 60 minutes and reweighed. The carbonate content is estimated by the loss in mass during this second firing, multiplied by 2.274 which is the molecular weight ratio between CaCO3 and CO2. The heavy metal and mineral composition was evaluated by ICP-AES and AAS.
 Results: The granulometric analyses show a sandy texture, according to the FAO classification. The organic matter content thus observed in the soils under the litter of these four species did not show any significant difference. The concentration of major mineral elements recorded in soils under the litter of Blighia welwitchii, Oncoba welwitschii, Zanthoxylum gilletii and Harungana madagascariensis did not show any significant difference. However, potassium, phosphorus, and magnesium have a high concentration compared to calcium and sodium. This study showed that the levels of cadmium, lead, arsenic and aluminum in the various samples of litter soils of all plant species including nickel for B. welwitschii are above the standards set by the Canadian Council of Ministers of the Environment for soil quality. Pollution factors for aluminum are the highest. This indicates that aluminum is the most polluting metal. The low pollution factors for lead and nickel are due to the low fixation of these metals by soils.
 Conclusions: Our study took place in the Luki Biosphere reserve and showed that the different soils under litter are polluted by very toxic and persistent heavy metals such as cadmium, lead, aluminum, arsenic and nickel. This study has revealed new aspects of heavy metal pollution. This pollution represents a serious threat to the environment in general and to humans in particular through the food chain.

Effective machine learning identification of TOC-rich zones in the Eagle Ford Shale

Successful hydrocarbon production in the Eagle Ford relies on technological advances such as directional geosteering, horizontal drilling, and hydraulic fracturing, as well as the identification and delineation of organic-rich intervals and fracture zones. Total organic carbon (TOC) is an excellent indicator for the organic richness and the hydrocarbon potential of shale in unconventional reservoirs; however, common methods for TOC estimation have many underlying assumptions and rely on empirical formulas. It is useful to develop a robust data-driven approach that could be used to reliably identify TOC-rich zones in unconventional plays such as the Eagle Ford. Using gamma-ray, deep resistivity, and sonic wireline well log data from La Salle County, South Texas, we generate a layer unit database and label the layer units using core measured TOC values. We apply a data-driven binary support vector machine (SVM) machine learning approach to identify TOC-rich zones within the Eagle Ford. We evaluate the performance of the SVM classifier and obtain F1 scores ranging from 97.4% to 99.4%. The methodology successfully identifies TOC-rich zones that match with geological observations, the ΔlogR method, and independently obtained core TOC measurements. We demonstrate the successful cross-well application of the methodology within the Eagle Ford Play Area and also demonstrate the successful cross-basin application of the methodology using data from the Barnett Shale Formation, Fort Worth Basin, North Texas, and the Duvernay Shale Formation of the West Canadian Sedimentary Basin, Canada.

Depositional environment and source rock quality of the Woodbine and Eagle Ford Groups, southern East Texas (Brazos) Basin: An integrated geochemical, sequence stratigraphic, and petrographic approach

X-ray fluorescence chemostratigraphy of the Cenomanian–Turonian Woodbine and Eagle Ford Groups in the southern parts of the East Texas Basin highlights significant mudstone chemical heterogeneities that commonly are difficult to observe or quantify at the macroscale. Several key elements, namely, Ca, Si, Mo, Mn, and Ni, were correlated to depositional conditions and used in a hierarchical cluster analysis to characterize five chemical facies (i.e., “chemofacies”) across 10 cored intervals of the Woodbine and Eagle Ford Groups: (1) argillaceous, organic-matter poor; (2) transitional, organic-matter poor; (3) transitional, organic-matter moderate; (4) calcareous, organic-matter rich; and (5) calcareous, organic-matter moderate. Characterizations of organic matter richness, mineralogy, and environmental conditions of deposition were established by correlating between key element abundances, total organic carbon measurements, x-ray diffraction measurements, and petrographic observations of lithologic composition, bioturbation, and sedimentary textures. Combined analysis of elemental geochemistry, stratigraphy, and petrographically observed sedimentary textures indicates that all chemofacies were deposited in an intrashelf basin above storm wave base. The most organic-rich chemofacies was deposited on a dominantly dysoxic distal shelf. Mudstone organic matter enrichment is driven dominantly by the minimization of siliciclastic dilution and secondarily enhanced by oxygen restriction. Regional correlations of chemofacies within a sequence stratigraphic framework developed from previous outcrop and subsurface work indicate a clear relationship between interpreted stratigraphy and chemofacies deposition. Generally, the highstand sequence sets of the Woodbine Group and upper Eagle Ford formation are dominated by mineralogically clay-rich, organic matter–lean, siliciclastic sedimentation and contain poor-quality source rock. Conversely, the transgressive sequence set of the lower Eagle Ford formation is dominated by organic matter–rich pelagic carbonate accumulation and contains excellent-quality source rock.

Source Rock Potential of Chichali and Samana Suk Formations Deposits in Panjpir Oilfield Subsurface, Punjab Platform, Pakistan

By using total organic carbon (TOC) and Rock-Eval pyrolysis analysis measurements, the hydrocarbon source rock potential of Chichali and Samana Suk formations found in the subsurface of Panjpir oilfield in Punjab platform located in the eastern part of the middle Indus Basin was investigated. Twenty two core samples were collected from producing well. The analysed samples of Chichali formation contains TOC ranging between 0.99-4.61 wt.% having average TOC of 1.51 wt.% and the S2 values of Rock-Eval show the poor to fair generative potential with values ranging from 0.99-3.08 mg HC/g rock. The samples have low hydrogen index values ranging from 21-302 mg HC/g TOC and also most of the samples have low T_(max ) values ranging from 422-432 °C and have OI values ranging from 15-82 mg CO2/g TOC. Samana Suk formation samples have TOC ranging between 0.28-1.38 wt.% having average TOC of 0.84 wt.%. S2 values of Rock-Eval shows poor generative potential with values ranging from 0.05-2.99 mg HC/g rock. The samples have low hydrogen index values ranging from 13-322 mg HC/g TOC and T_(max) values ranging from 423-435 °C, and have OI values ranging from 41-182 mg CO2/g TOC. On the basis of analysis performed only one sample from Chichali and five samples of Samana Suk formations have entered early maturity zone, while all remaining samples lie in immature zone as indicated by HI vs T_(max) plot. HI vs OI plot and HI vs T_ (max) indicates the presence of kerogen Type III. All of the samples from Samana Suk formation shows poor generative potential as compared to Chichali formation having fair generative potential as indicated by S2 vs TOC plot. Hence, from the results some minor gas could be expected to have been generated from Chichali formation in Panjpir oilfield subsurface.

Lithological Parameters Controlling Rock Strength and Elastic Properties of Peritidal and Deep Marine Carbonate Mudrocks, Lower to Upper Jurassic Succession, Central Saudi Arabia

The study integrated lithofacies analysis and measurement of total organic carbon "TOC," porosity, and mechanical properties to evaluate the main factors controlling rock strength and elastic properties of three carbonate mudrocks units within the Jurassic succession of Central Saudi Arabia. Textural and microstructural analyses revealed that the former two units (Hanifa Formation Hawtah Member and Tuwaiq Formation) have five lithofacies interpreted as a lower shoreface intra-shelf basin deposition, respectively. Two mudrock lithofacies within the Upper Marrat Formation were recognized, both deposited under peritidal low ramp setting. Weak to moderate correlations between mechanical properties and porosity in all studied formations were observed; coefficient of determination R2 values range between 0. 1 and 0.7. Tensile strength has the strongest correlation with porosity and mineral composition. Hard phase mineral (quartz, feldspar, and pyrite) abundance has a more robust correlation with elastic moduli compared to the other minerals. Relatively higher R2 values were observed for the correlations between rock strength and clay + TOC content in Tuwaiq and Hanifa compared with Marrat mudrocks. Marrat and Tuwaiq mudrocks lithofacies have a stronger correlation between particle size and unconfined compressive strength, whereas particle size is weakly correlated with elastic moduli. Sedimentary layering and associated anisotropy significantly control these correlations. Deep lower shoreface deposits of Hanifa mudrock are mechanically stiffer than intra-shelf basin outer ramp deposits of Tuwaiq mudrock lithofacies. Peritidal Upper Marrat mudrock lithofacies have slightly higher stiffness than Tuwaiq mudrock and lower stiffness than Hanifa mudrock. The results are useful to predict the rock brittleness of these Jurassic intervals and their worldwide equivalent.

Amine-rich quartz nanoparticles for Cu(II) chelation and their application as an efficient catalyst for oxidative degradation of Rhodamine B dye.

The study describes the loading of the quartz SiO2 nanoparticles (NPs) with (3-aminopropyl)triethoxysilane (APTES) linker with simultaneous lengthening of the linker through the terminal amine group by glutaraldehyde (GA). The reactive polyethylenimine (PEI) was introduced to the surface to increase the ability to capture Cu(II) ions. The composite got the abbreviation SiO2/PEI-Cu(II). The Cu(II) ions were the active center with a peroxo-complex activation state. The composite characterization included scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron-dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), thermogravimetric analysis (TGA), and Brunauer-Emmett-Teller (BET) surface analyzer. The kinetics of the oxidative degradation of Rhodamine B (RhB) dye obeyed the pseudo-first order under flooding conditions. The reaction parameters including the catalyst dose, solution pH, initial concentration of reactants, and temperature got some attention. The obtained results showed that more than 91.7 ± 1% of RhB dye was degraded to CO2, NH4+, NO3-, H2O, and some inorganic acids after 30 min as confirmed by gas chromatography mass spectrometry and total organic carbon (TOC) measurements. Also, GC-MS spectra for water samples drawn from the reaction in successive periods had suggested a conceivable degradation pathway for RhB by hydroxyl radicals. Degradation starts with de-alkylation then carboxyphenyl removal followed by two successive ring-opening stages. Both the effects of the catalyst recycling and treated water reusability on the reaction rate were studied. The catalyst provided noticeable stability over three consecutive cycles.

Gamma-irradiation-induced molecular-weight distribution and complexation affinity of humic acid with Cs+, Sr2+, and Eu3+

Solutions of humic acid (HA) were irradiated with 0, 1, 5, 10, 50, and 100 kGy of gamma irradiation using a 60Co source. The non-irradiated and irradiated HA molecules were fractionated by ultrafiltration into four categories: > 100, 50–100, 10–50, and < 10 kDa. Total organic carbon measurements and potentiometric titration analysis suggested that (1) some gamma-irradiated HA molecules were degraded into smaller molecules and (2) radiolytic degradation caused phenolic –OH became the predominant functional group in the small molecular-weight fractions of HA. The effect of absorbed dose of gamma rays on the distributions of Cs+, Sr2+, and Eu3+ ions in the molecular-weight fractions of the metal–HA systems was examined to discuss the complexation affinity. The metal ions were distributed in the smaller molecular-weight fractions at different doses, which corresponded to the degradation of HA molecules. For a predetermined absorbed dose, Cs+ ions did not change the molecular-weight distribution of the total organic carbon content of the degraded HA molecules. Conversely, the Sr2+ and Eu3+ ions redistributed organic carbon toward the larger molecular-weight fractions.

Measurement methods of total organic carbon in seawater

Total organic carbon (TOC) can reflect the total amount of organic matter in water. This paper introduces the common methods of measuring organic carbon, including high temperature combustion method, potassium persulfate oxidation method, spectrometry, ozone oxidation chemiluminescence method, supercritical water oxidation method and so on. At present, high temperature combustion method is the most widely used method for TOC measurement in seawater, because of its high oxidation efficiency. TOC sensor needs to be developed to realize in-situ and long-term monitoring.

Integration of Nuclear Spectroscopy Technology and Core Data Results for Through-Casing TOC Measurement and Saturation Analysis: A Case Study in Najmah-Sargelu Reservoir, South Kuwait

The acquisition of openhole logging data is not always guaranteed because of difficult drilling environments. In such cases, formation evaluation, and thus the completion program, becomes a real challenge. The situation becomes more complex when dealing with unconventional reservoirs with very tight carbonates and organic carbon-rich formations. This paper presents a method to measure the total organic carbon (TOC), which, in this paper, represents the organic carbon in the matrix (kerogen and coal), and to estimate oil saturation in such a challenging environment. A suite of wireline tools (gamma ray (GR), Spectralog, density, neutron, nuclear spectroscopy) was run through 7.625-in. casing to evaluate the formation and to quantify TOC and the oil in the pores. The nuclear spectroscopy tool, which was the master tool, measures the total carbon in the formation. Part of this carbon is attributed to the inorganic matrix (carbonates). Another part is attributed to the organic matter in the matrix (kerogen). The remaining carbon, or excess carbon, is mainly the carbon inside the pores. The process consists of integrating the conventional logging data, spectroscopy data, core data, and some geological constraints to estimate corrected porosity, mineralogy, and TOC in the kerogen-rich intervals. The excess carbon, which is not attributed to the matrix and TOC, is used to estimate oil saturation. Finally, core data are used to validate the analysis results. The presented methodology has been applied to a casedhole well with no openhole data previously acquired due to drilling issues. The primary target of the well, in the deep section, produced water; then, the operator decided to revisit the second target and complete it for testing. It has to be pointed out that over the well-cemented intervals, the results showed a very good matching of the corrected total porosity and the core total porosity. Relying on TOC and saturation analysis results, the operator selected the most promising intervals to be tested. Testing results have shown excellent matching between production results and oil saturation analysis results. TOC and oil saturation quantification using nuclear spectroscopy technology and core data results showed its success in both tight carbonates and organic carbon-rich reservoirs. This method will be a solution to evaluate and complete any wells with no openhole data acquired, and also to evaluate and complete unconventional formations where the conventional methods have shown their limitations.

Effect of reservoir characteristics on the productivity and production forecasting of the Montney shale gas in Canada: Discussion

Abstract Kim et al. (2019) recently presented an analysis of the influence of reservoir and completion parameters on natural gas production from wells drilled and completed in the Montney Formation in Alberta, Canada. A key finding of their study is that one of the reservoir quality parameters, total organic carbon (TOC), has a strong positive linear relationship with peak monthly gas rate. However, their data set incorrectly includes a TOC measurement of a drill-core sample acquired from the unrelated Jurassic Nordegg Member, which unconformably overlies the Triassic Montney Formation. Excluding this single inapplicable Nordegg sample from the Montney data set results in peak monthly gas rate having essentially no significant correlation with TOC, and calls into question the proposal of Kim et al. that productivity in the unconventional Montney gas play can quantified and forecasted solely on the basis of organic carbon content parameters.

ZnO-Based Catalyst for Photodegradation of 2-Chlorophenol in Aqueous Solution Under Simulated Solar Light Using a Continuous Flow Method

ZnO nanoparticles, stacked on the bottom of a glass dish, were used as a catalyst for the photodegradation of aqueous 2-chlorophenol (2-CP) contaminant. Solutions of 2-CP at different concentrations and pH values were passed over the ZnO film under simulated solar light. The effect of the light intensity on the contaminant photodegradation rate was investigated. The photodegradation efficiency was evaluated based on the percentage degradation, turnover number, turnover frequency, and quantum yield. The reaction efficiency parameters showed no significant variation when changing the pH across moderate values (neutral, slightly basic, and slightly acidic). Complete mineralization of the contaminant to CO2, H2O, and other minerals was confirmed by various analytical methods including high-performance liquid chromatography, ultraviolet–visible (UV–Vis) spectroscopy, and total organic carbon measurements. The continuous flow method applied in this work showed promising results in terms of safe removal of 2-CP from water at laboratory scale. More study of this method is needed to enable its use at larger, pilot plant scale.

Zn/La Mixed Oxides Prepared by Coprecipitation: Synthesis, Characterization and Photocatalytic Studies.

Mixed oxides containing zinc and lanthanum were prepared by coprecipitation in alkaline medium, followed by calcination at 400 °C. The initial precipitation product and the calcined form were characterized by Brunauer–Emmett–Teller (BET) method adsorption of nitrogen at −196 °C, Scanning Electron Microscopy/Electron-Probe Microanalysis (SEM/EPM), Ultraviolet—Diffuse Reflectance Spectroscopy (UV-DRS) and Infrared (IR) spectroscopy. The band gap slightly changes from 3.23 eV to 3 eV by calcination. The photocatalytic performance of the solids were investigated in diluted aqueous medium, by using clofibric acid (CA), a stable and toxic molecule used as precursor in some pesticides and drugs, as test compound, possibly found in the wastewaters in low concentrations. The effects of the degradation extent, determined by high performance liquid chromatography (HPLC) and total organic carbon (TOC) measurements, were investigated at different initial concentrations of CA. Within about 60 min the CA degradation is almost total at low concentration values (3 ppm) and reaches over 80% in 180 min for an initial concentration of 50 ppm. Moreover, the CA removal performance of photocatalyst remains excellent after three cycles of use: the removal yield was practically total after 60 min in the first two cycles and reached 95% even in the third cycle.

Tracing the paleo-methane seepage activity over the past 20,000 years in the sediments of Qiongdongnan Basin, northwestern South China Sea

The seepage activity of paleo-methane has been proven to exist in geological history and play an important role in the evolution of the Earth's environment. This study reports grain size, major/trace elements, total nitrogen (TN), total carbon (TC), total organic carbon (TOC), total sulfur (TS), magnetic susceptibility and AMS-14C measurements for sediment samples in a drill core (~282 cm long; Site Q6 at ~1400 m water depth) from the ‘Haima seep’ sedimentary area in the Qiongdongnan Basin, along the northern slope of the South China Sea (SCS). The alternative index system for paleo-methane seepage identification was established through testing and analysis, and three methane release events (MREs) were successfully identified: 254–282 cm (MRE1: 19.3–17.8 ka), 144–162 cm (MRE2: 11. 9–10.8 ka) and 90–124 cm (MRE3: 10.0–8.5 ka). When methane seepage occurred, the enrichment of authigenic carbonate minerals (high Mg-calcite or aragonite) led to the increase in the content of CaO and ‘dilution’ in the total rare earth element content (∑REE). However, the occurrence of authigenic pyrite resulted in a significant increase in TS and the total sulfur/total organic carbon ratio (S/C) in the sediments, and a synchronous decrease in the magnetic susceptibility. Meanwhile, the change of redox environment also induced the enrichment of Mo, U, and the positive anomaly of δCe. Based on the records of methane release events, the control mechanisms for the different time scales and different periods, such as sea level change, sea floor temperature change, and turbidity current activity were preliminarily discussed. Finally, the history of methane seepage activity was reconstructed, and conceptual diagrams were drawn of the study area encompassing the last 20 ka.

The diatom response to Postglacial environments in the White Sea, the European Arctic

The White Sea is a small semi-enclosed Arctic sea influenced by Atlantic waters. It was completely covered by the Scandinavian Ice Sheet in the Late Pleistocene and plays a key role in the reconstruction of the degradation of the Scandinavian Ice Sheet and Atlantic Water advection into the Arctic Ocean. We examined the inflow of Atlantic water into the White Sea Basin as the leading feature of postglacial sedimentation processes. Palaeoreconstructions were conducted through detailed studies of diatom assemblages in two sediment cores from the central area (PS-6042) and outer part (PS-6050) of Dvina Bay. Stratigraphic division of the core sediments was performed on the basis of palynostratigraphy and accelerator mass spectrometry 14C dates. The composition of diatom assemblages in postglacial sediments from Dvina Bay indicate a change in the environment from a freshwater sea bay to fully marine conditions over the past 12 cal kyr. Based on the obtained results, we established that the Atlantic water started to flow into the central Dvina Bay in the first half of the Preboreal (11.7–11.3 cal ka BP), and the greatest increase in water surface temperatures in central Dvina Bay occurred during the period from the end of the Atlantic to the first half of the Subboreal. We confirmed these conclusions through comparison with previously obtained results of aquatic palynomorphs, pollen and spores, grain size analysis, and measurements of total organic carbon and biogenic silica contents, as well as through correlation with published palaeoreconstructions of the White Sea and the Arctic Ocean.

Photocatalytic degradation of cephalexin by UV activated persulfate and Fenton in synthetic wastewater: optimization, kinetic study, reaction pathway and intermediate products.

We used Low pressure mercury vapor lamp activated of Sodium Persulfate (UV/SPS) and Fenton processes in two separate reactors to comparison of cephalexin (CPX) degradation in aqueous solution. The effect of pH, initial concentration of SPS, concentration of CPX, concentration of H2O2 and concentration of Fe2+ on the degradation of CPX were investigated. The residue of CPX and metabolites were determined by HPLC and GC/MS. The Total Organic Carbon (TOC) analysis was utilized for surveying the mineralization of CPX. Biodegradability of CPX in both advanced oxidation processes was evaluated by BOD5/COD in optimum condition. The results indicated that the maximum CPX removal was obtained at pH3, H2O2 3mM, concentration of initial CPX 10mg/L and by increasing the doses of SPS from 0.1 to 0.2mM, the degradation of CPX was enhanced. In this study, the most important factors for AOP efficiency was concentration of initial CPX; and then pH in UV/SPS and H2O2 in Fenton processes. The TOC measurements indicate that the UV/SPS and Fenton can efficiently mineralize CPX. CPX removed enough to achieve suitable biodegradability for a further biological process. Too, analysis of generated intermediates during the degradation of CPX was conducted by GC/MS method and a degradation pathway was proposed.

Data-Driven Approaches to Predict Thermal Maturity Indices of Organic Matter Using Artificial Neural Networks.

Prediction of thermal maturity index parameters in organic shales plays a critical role in defining the hydrocarbon prospect and proper economic evaluation of the field. Hydrocarbon potential in shales is evaluated using the percentage of organic indices such as total organic carbon (TOC), thermal maturity temperature, source potentials, and hydrogen and oxygen indices. Direct measurement of these parameters in the laboratory is the most accurate way to obtain a representative value, but, at the same time, it is very expensive. In the absence of such facilities, other approaches such as analytical solutions and empirical correlations are used to estimate the organic indices in shale. The objective of this study is to develop data-driven machine learning-based models to predict continuous profiles of geochemical logs of organic shale formation. The machine learning models are trained using the petrophysical wireline logs as input and the corresponding laboratory-measured core data as a target for Barnett shale formations. More than 400 log data and the corresponding core data were collected for this purpose. The petrophysical wireline logs are γ-ray, bulk density, neutron porosity, sonic transient time, spontaneous potential, and shallow resistivity logs. The corresponding core data includes the experimental results from the Rock-Eval pyrolysis and Leco TOC measurements. A backpropagation artificial neural network coupled with a particle swarm optimization algorithm was used in this work. In addition to the development of optimized PSO-ANN models, explicit empirical correlations are also extracted from the fine-tuned weights and biases of the optimized models. The proposed models work with a higher accuracy within the range of the data set on which the models are trained. The proposed models can give real-time quantification of the organic matter maturity that can be linked with the real-time drilling operations and help identify the hotspots of mature organic matter in the drilled section.

Degradation of cimetidine by oxidative processes, mass spectrometry products elucidation and toxicity evaluation

The use of pharmaceuticals has gradually increased and they have become a concern due to the ecological potential impact. Cimetidine (CIM), employed in the treatment of gastrointestinal disorders, is detected frequently in waters worldwide. In this study, CIM aqueous solutions were exposed to four oxidative processes: chlorination (NaClO), ozonation (O3), photocatalysis (UV/TiO2) and photolysis (UV). Low removal of organic matter was observed by total organic carbon measurement. CIM removal was determined by mass spectrometry. CIM was completely degraded in the chlorination and ozonation experiments but not by photodegradation. The results indicate that CIM removal occurs by transformation into persistent degradation products. Seven products, among them five have until now not been reported, were elucidated throughout the experiments by high resolution mass spectrometry and the CIM degradation reaction pathways were proposed. The degradation products were mainly formed by the oxidation of thioether, addition of hydroxyl radicals and oxidative cleavage. No difference in MTT cytotoxicity against HepG2 cells between the treated and untreated CIM solutions was observed. For solutions treated by photolysis, a trend of decreased cell viability with increasing concentration was observed. The ECOSAR software was used to estimate the toxicity of degradation products by structure-activity relationship. Among the identified products only one (CIM-97 - C5H8N2) was considered harmful for the organisms evaluated. The toxicity may be attributed to the presence of the imidazole group, present in molecules of biological importance and used in pharmaceutical industry.

Regional hydrocarbon potential and thermal reconstruction of the Lower Jurassic to lowermost Cretaceous source rocks in the Danish Central Graben

The Danish part of the Central Graben (DCG) is one of the petroliferous basins in the offshore region of north-western Europe. The source rock quality and maturity is here reviewed, based on 5556 Rock-Eval analyses and total organic carbon (TOC) measurements from 78 wells and 1175 vitrinite reflectance (VR) measurement from 55 wells, which makes this study the most comprehensive to date. The thermal maturity is evaluated through 1-D basin modelling of 46 wells. Statistical parameters describ-ing the distribution of TOC, hydrocarbon index (HI) and Tmax are presented for the Lower Jurassic marine Fjerritslev Formation, the Middle Jurassic terrestrial-paralic Bryne, Lulu, and Middle Graben Formations and the Upper Jurassic to lowermost Cretaceous marine Lola and Farsund Formations in six areas in the DCG. For the Farsund Formation the source-rock richness is presented for selected stratigraphic sequences. The upper part of the Farsund Formation is immature in the southern part of the Salt Dome Province, and late oil mature in and near the Tail End Graben and in the Søgne Basin. The lower part of the Farsund Formation is immature in local areas, yet post-mature in the Tail End Graben and in the Salt Dome Province. The Lower and Middle Jurassic shales are gas-prone in most of the DCG. The depth of the oil window, as defined by a VR of 0.6% Ro, ranges between 2200 and 4500 m. The variations are ascribed to heat flow differences in the DCG and can be modelled by a simple depth model, which includes the thickness of the Cretaceous to Palaeo-gene Chalk and Cromer Knoll Groups. According to the model, a thick Chalk Group offsets the oil window to deeper levels, which likely can be attributed to the thermal properties of the highly thermally conductive chalk compared to the underlying less thermally conductive clays. The DCG is an overpressured basin, and high-pressure, high-temperature conditions are expected to occur deeper than 3.8 km except for the Feda and Gertrud Grabens where such conditions, due to generally lower tem-peratures, are expected to occur deeper than around 4.7 km.

Geochemical characterization and origin of crude oils in the Oriente basin, Ecuador, South America

The Cretaceous oil reservoir located in eastern slope belt of the Oriente basin accounts for most of the discoveries in last decade in Ecuador, which makes the Oriente basin one of the most important oil exploration targets in South America. Crude oil samples (n = 31) in 31 wells together with mudstone and limestone source rocks (n = 18) from Cretaceous Napo Formation in 16 wells were analyzed to evaluate the geochemical characteristics of the oil reservoir oil.Geochemical analyses included measurements of total organic carbon (TOC) content, Rock-Eval Pyrolysis, gas chromatography (GC), and gas chromatography-mass-spectrometry (GC-MS).All the oil samples have pre-uimodal n-alkane distribution dominated by lower molecular weight components (peak at C15–C17) with a small peak at C25–C30. The carbon preference index (CPI) and odd-over-even predominance (OEP) values range between 1.0 and 1.34, and 1.0–1.21 respectively; Pr/Ph ratios range from 0.67 to 1.16; high Pr/n-C17 (0.80–3.47) and Ph/n-C18 ratios (0.82–7.86) values and dominate C27 regular steranes, all these biomarkers show that the oil derived from marine algal material. Furthermore, all oils have similar Terpanes and Steranes distribution shape, peak at C23TT, and low at C22TT (TT = tricyclic terpanes), relative low C22/C21, C24/C23 and C26/C25 tricyclic terpane ratios, higher C27R (R = regular steranes) content than C29R and C28R. These biomarkers demonstrate that all the oils are from same genetic family although they came from different zones. There are two kinds of source rocks in the Oriente basin, shale and argillaceous bioclastic limestone of Napo Formation. These rocks are good-excellent mature according to TOC and Rock-Eval assessment. The two source rocks show obvious different Terpanes and Steranes distribution shape in mz191 and mz217 maps. The Oil-Source correlation analysis demonstrates that the crude oils have similar Terpane and Steranes distribution shape and biomarker value, especially the C27R–C28R–C29R ratio, with argillaceous bioclastic limestone of Napo Formation. This new geochemical data suggests that the argillaceous bioclastic limestone is the major source rock in the Oriente basin. Thus, distribution of this stratigraphic unit should be the key point for future exploration.