Caracterização petrográfica e litogeoquímica de granitoides ediacaranos no extremo NE da Província da Borborema (NE do Brasil) com ênfase nos plútons Gameleira, Pitombeira e Taipu

The studied area is situated in the northeastern extremity of the Rio Grande do Norte State, between the municipalities of Taipu and Poço Branco, and is geologically inserted into the São José do Campestre Crystalline Terrain within the Borborema Province, where the analysis of field relationships, petrographic and geochemical data allowed the distinction of three plutons named: Gameleira, Taipu and Pitombeira. The Gamaleira Pluton is composed of granodioritic rocks characterized by zoned plagioclase phenocrysts, with amphibole and biotite as the main mafic phases. Geochemically, these are metaluminous rocks of calc-alkaline nature and magnesian character. The Pitombeira Pluton encompasses two facies: (a) a coarse-grained to porphyritic monzo- to syenogranitic facies marked by K-feldspar phenocrysts; and (b) a quartz dioritic to tonalitic facies with partially zoned plagioclase laths showing chilled rims. Geochemically, rocks of the monzo- to syenogranitic facies are transitional between metaluminous and peraluminous, display a subalkaline nature (high K calc-alkaline) and a ferroan character, whereas rocks of the quartz dioritic to tonalitic facies are metaluminous, with shoshonitic affinity and ferroan character. Lastly, the Taipu Pluton is made of monzoto syenogranitic rocks with biotite as the chief mafic mineral. They are peraluminous rocks of subalkaline nature (high-K calc-alkaline) and ferroan character. Regarding the rare-earth elements (REE), it is possible to conclude that the three studied plutons display negative Eu anomalies and a relative enrichment of LREE over HREE, with LaN/YbN ratios between 9.39 to 16.20 (Gameleira Pluton), 17.99 to 31.39 (granitic facies of the Pitombeira Pluton), 14.15 to 21.81 (dioritic facies of the Pitombeira Pluton) and 15.17 to 175.41 (Taipu Pluton). Based on the combined investigation of geochemical data and discrimination tectonic diagrams, a late- to post-collisional tectonic environment is suggested for the plutons here studied

Estudo da incorporação de resíduos de perfuração para aplicação em cimentação de poços de petróleo

During the drilling of oil and natural gas are generated solid waste, liquid and gaseous. These solid fragments, which are known as cuttings, are carried to the surface through the drilling fluid. Furthermore, this fluid serves to cool the bit, keeping the internal pressure of the well, and others. This solid residue is very polluting, because it has incorporated beyond the drilling fluid, which has several chemical additives harmful to the environment, some heavy metals that are harmful to the environment, such as lead. To minimize the residue generated, are currently being studied numerous techniques to mitigate the problems that such waste can cause to the environment, like addition of cuttings in the composition of soil cement brick masonry construction, addition of cuttings on the clay matrix for the manufacture of solid masonry bricks and ceramic blocks and coprocessing of the cuttings in cement. So, the main objective of this work is the incorporation of cuttings drilling of oil wells, the cement slurry used in the cementing operation of the well. This cuttings used in this study, arising from the formation Pendências, was milled and separated in a sieve of 100 mesh. After grinding had a mean particle sike in order of 86 mm and crystal structure containing phases of quartz and calcite type, characteristic of the Portland cement. Were formulated and prepared slurries of cement with density 13 lb / gal, containing different concentrations of gravel, and realized characterization tests API SPEC 10A and RP 10B. Free water tests showed values lower than 5.9% and the rheological model that best described the behavior of the mixtures was the power. The results of compressive strength (10.3 MPa) and stability (Dr <0.5 lb / gal) had values within the set of operational procedures. Thus, the gravel from the drilling operation, may be used as binders in addition to Portland cement oil wells, in order to reuse this waste and reduce the cost of the cement paste.

Uso de água produzida na formulação de fluidos de perfuração

Drilling fluids have fundamental importance in the petroleum activities, since they are responsible for remove the cuttings, maintain pressure and well stability, preventing collapse and inflow of fluid into the rock formation and maintain lubrication and cooling the drill. There are basically three types of drilling fluids: water-based, non-aqueous and aerated based. The water-based drilling fluid is widely used because it is less aggressive to the environment and provide excellent stability and inhibition (when the water based drilling fluid is a inhibition fluid), among other qualities. Produced water is generated simultaneously with oil during production and has high concentrations of metals and contaminants, so it’s necessary to treat for disposal this water. The produced water from the fields of Urucu-AM and Riacho da forquilha-RN have high concentrations of contaminants, metals and salts such as calcium and magnesium, complicating their treatment and disposal. Thus, the objective was to analyze the use of synthetic produced water with similar characteristics of produced water from Urucu-AM and Riacho da Forquilha-RN for formulate a water-based drilling mud, noting the influence of varying the concentration of calcium and magnesium into filtered and rheology tests. We conducted a simple 32 factorial experimental design for statistical modeling of data. The results showed that the varying concentrations of calcium and magnesium did not influence the rheology of the fluid, where in the plastic viscosity, apparent viscosity and the initial and final gels does not varied significantly. For the filtrate tests, calcium concentration in a linear fashion influenced chloride concentration, where when we have a higher concentration of calcium we have a higher the concentration of chloride in the filtrate. For the Urucu’s produced water based fluids, volume of filtrate was observed that the calcium concentration influences quadratically, this means that high calcium concentrations interfere with the power of the inhibitors used in the formulation of the filtered fluid. For Riacho’s produced water based fluid, Calcium’s influences is linear for volume of filtrate. The magnesium concentration was significant only for chloride concentration in a quadratic way just for Urucu’s produced water based fluids. The mud with maximum concentration of magnesium (9,411g/L), but minimal concentration of calcium (0,733g/L) showed good results. Therefore, a maximum water produced by magnesium concentration of 9,411g/L and the maximum calcium concentration of 0,733g/L can be used for formulating water-based drilling fluids, providing appropriate properties for this kind of fluid.

Avaliação da variação sedimentológica em uma área da plataforma continental sob a atuação da indústria petrolífera

Petroleum exploration activity occurs on the offshore Potiguar Basin, from very shallow (2-3 m) until about 50 m water depth, extending from Alto de Touros (RN) to Alto de Fortaleza (CE). Take in account the biological importance and the heterogeneity of sediments on this area, it is necessary the understanding of the sedimentological dynamics, and mainly the changes generated by petroleum exploration to prevent possible damages to environment. Despite the intense activity of oil exploration in this area, research projects like these are still rare. In view to minimize this gap, this study was developed to evaluate sedimentological, mineralogical and geochemical changes in the vicinity of a exploration well, here designated as well A, located on the Middle continental shelf, near the transition to Outer shelf. The well selected for this study was the first one drilled with Riserless Mud Recovery technology (RMR) in Brazil. The main difference from this to the conventional method is the possibility of drilling phase I of the well with return of drilling material to the rig tank, minimizing fluid and gravel discharging around the vicinity, during this phase. Monitoring consisted of three surveys, first of them done before start drilling, the second one done 19 days after the end of drilling and the third one done one year after then. Comparison of the studied variables (calcium carbonate and organic matter content, sediment size, mineralogy and geochemistry) was done with their average, median and coefficient of variation values to understand the changes after drilling activity. Because operating company technical reasons, the well location was changed after the first survey (C1), resulting in a shift of the sampled area on the two last surveys (C2 e C3). Nevertheless, the acquired data presented a good correlation, with no loss to the mean goal of the study. The sedimentological, mineralogical and geochemical analyzes were done at Federal University of Rio Grande do Norte (UFRN). The results indicated a predominantly sandy environment along the three surveys. It was noticed that the first survey (C1), presented different values for all the studied variables than to the second (C2) and third (C3) surveys, which had similar values. Siliciclastic sediments are prevalent at all surveys, and quartz is the main component (more than 80%). Heavy minerals (garnet, turmaline, zircon and lmenite), rock fragments and mud aggregates also was described. Bioclastic sediments are dominated by coralline algae (more than 45%) and mollusks (more than 30%), followed by benthic foraminifera, bryozoans and worm tubes. More rarely was observed ostracoda and spike of calcareous sponge. Because the low changes of the sediments at the studied area and by the using of RMR method in the drilling, it was possible to conclude that drilling activity did not promote significant alteration on the local sediment cover. Changes in the studied variables before and after drilling activity could be influenced by the changing in the sampling area after survey 1 (C1).

Análise estratigráfica de subsuperfície do Devoniano Inferior da Bacia do Rio do Peixe, Nordeste do Brasil

Subsurface stratigraphic analysis of Devonian strata from the Rio do Peixe Basin, newly recognized by palynological studies, has resulted in the identification of two new lithostratigraphic units assembled in the Santa Helena Group. The Pilões Formation, the lower unit, is composed mainly of dark mudstones and medium-tovery fine-grained sandstones, with minor conglomerates and breccias. The Triunfo Formation, the upper unit, comprises whitish grey, kaolinitic, coarse-grained to conglomeratic, cross stratified sandstones and conglomerates, with interbedded mudstones and fine-grained sandstones. These units were characterized using cores, sidewall and cuttings samples, conventional logs and image log, from three wells drilled by PETROBRAS, and 3D seismic data. The Pilões Formation is interpreted as prodeltaic facies, with lesser associated subaqueous talus, debrite and sandy turbidite lobe facies, distal part of fandelta and braided fluviodeltaic facies of Triunfo Formation. The Santa Helena Group corresponds to the Lower Devonian tectono-sequence deposited in a NW-SE-trending graben during a transgressiveregressive cycle. With 343 meters of thickness (isochore) in well 1-PIL-1-PB (Pilões 1), this sequence has a non-conformity at the lower boundary and its upper boundary is an unconformity with the Lower Cretaceous tectono-sequence (Rio do Peixe Group), that represents a hiatus of about 265 million years. Ignimbrites and coignimbrite breccias (Poço da Jurema volcanic breccia), related to an unknown pyroclastic volcanic event, were recognized at the northern margin of the Sousa halfgraben. Evidence from well data suggests that this event is coeval with the Devonian graben filling. The present study indicates a polyhistorical tectono-volcanosedimentary evolution of the basin. This lithostratigraphic update brings new perspectives for geological research in the Rio do Peixe Basin, as well as in other inland basins of the Northeastern of Brazil. The results of the research also contribute to the kwnoledge of the Borborema Province and western Gondwana paleogeography during the Early Devonian.

Otimização dos parâmetros de um modelo de bomba em sistemas de bombeio centrífugo submerso

One of several techniques applied to production processes oil is the artificial lift, using equipment in order to reduce the bottom hole pressure, providing a pressure differential, resulting in a flow increase. The choice of the artificial lift method depends on a detailed analysis of the some factors, such as initial costs of installation, maintenance, and the existing conditions in the producing field. The Electrical Submersible Pumping method (ESP) appears to be quite efficient when the objective is to produce high liquid flow rates in both onshore and offshore environments, in adverse conditions of temperature and in the presence of viscous fluids. By definition, ESP is a method of artificial lift in which a subsurface electric motor transforms electrical into mechanical energy to trigger a centrifugal pump of multiple stages, composed of a rotating impeller (rotor) and a stationary diffuser (stator). The pump converts the mechanical energy of the engine into kinetic energy in the form of velocity, which pushes the fluid to the surface. The objective of this work is to implement the optimization method of the flexible polyhedron, known as Modified Simplex Method (MSM) applied to the study of the influence of the modification of the input and output parameters of the centrifugal pump impeller in the channel of a system ESP. In the use of the optimization method by changing the angular parameters of the pump, the resultant data applied to the simulations allowed to obtain optimized values of the Head (lift height), lossless efficiency and the power with differentiated results.

Recuperação avançada de óleos pesados em poços fraturados utilizando aquecimento eletromagnético indutivo

The success achieved by thermal methods of recovery, in heavy oils, prompted the emergence of studies on the use of electromagnetic waves as heat generating sources in oil reservoirs. Thus, this generation is achieved by three types of different processes according to the frequency range used. They are: the electromagnetic induction heating, the resistive and the dielectric, also known as radiation. This study was based on computer simulations in oil reservoirs with characteristics similar to those found in the sedimentary basins of the Brazilian Northeast. All cases studied were simulated using the software STARS, CMG (Computer Group, version 2012.10 Modeling). Some simulations took into account the inclusion of electrically sensitive particles in certain sectors of the reservoir model studied by fracturing. The purpose of this work is the use of the electromagnetic induction heating as a recovery method of heavy oil, to check the influence of these aforementioned particles on the reservoir model used. Comparative analyses were made involving electromagnetic induction heating, the operation of hydraulic fracturing and the injection of water to the different situations of the reservoir model studied. It was found that fracturing the injection well in order that the electromagnetic heating occurs in the same well where there is water injection, there was a considerable increase in the recovery factor and in the cumulative oil production in relation to the models in which hydraulic fracturing occurred in the production well and water injection in the injection well. This is due to the generation of steam in situ in the reservoir.

Aplicação de nanoemulsão ácida em acidificação de poços de petróleo

A constante busca da indústria de petróleo pelo aumento de produção à um baixo custo operacional faz necessário o desenvolvimento de tecnologias que una as duas necessidades. A Acidificação de matriz é um método de estimulação frequentemente empregado para aumentar produção de um poço de petróleo com um custo menor se comparado a um fraturamento. O objetivo deste trabalho é estudar a obtenção de nanoemulsões ácidas para aplicação em acidificação de matriz. As nanoemulsões são capazes de retardar reações, por diminuir a difusão do ácido no meio, possibilitando a acidificação em reservatórios com baixa permeabilidade. Os reagentes utilizados para formar os sistemas nanoemulsionados foram UNT L90/OMS e RNX 110 como tensoativos, Sec-butanol como cotensoativo, Xileno e Querosene como fase óleo e Solução de HCl como fase aquosa. As nanoemulsões foram obtidas a partir da diluição de microemulsões com água ou solução de HCl. Foi realizado estudo das tensões superficiais, estudo das cinéticas de reação, avaliação da injeção em rocha carbonática e remoção de borra asfáltica. As nanoemulsões apresentaram tensão superficial menor que suas microemulsões de origem. As nanoemulsões tiveram êxito em retardar a reação entre CaCO3 e HCl, onde o sistema mais eficiente é composto por UNT L90/OMS, Secbutanol, Querosene e solução de HCl. As nanoemulsões foram eficientes em formar wormholes em plugs de carbonato calcitico com baixa permeabilidade natural. As wormholes proporcionaram incremento de permeabilidade alcançando valores de até 390 mD. O sistema ácido apresentou bom resultado de remoção de borra asfáltica, mostrando o potencial das nanoemulsões em remover esse tipo de dano. Conclui-se que os sistemas nanoemulsionados têm grande potencial de aplicação em acidificação de matriz.

Análise de desempenho de algoritmos de compressão de dados com perda para aplicações industriais

The great amount of data generated as the result of the automation and process supervision in industry implies in two problems: a big demand of storage in discs and the difficulty in streaming this data through a telecommunications link. The lossy data compression algorithms were born in the 90’s with the goal of solving these problems and, by consequence, industries started to use those algorithms in industrial supervision systems to compress data in real time. These algorithms were projected to eliminate redundant and undesired information in a efficient and simple way. However, those algorithms parameters must be set for each process variable, becoming impracticable to configure this parameters for each variable in case of systems that monitor thousands of them. In that context, this paper propose the algorithm Adaptive Swinging Door Trending that consists in a adaptation of the Swinging Door Trending, as this main parameters are adjusted dynamically by the analysis of the signal tendencies in real time. It’s also proposed a comparative analysis of performance in lossy data compression algorithms applied on time series process variables and dynamometer cards. The algorithms used to compare were the piecewise linear and the transforms.

Estudo de simulação de reservatórios para o desenvolvimento de um campo do nordeste brasileiro

In the last 16 years emerged in Brazil a segment of independent producers with focus on onshore basins and shallow waters. Among the challenges of these companies is the development of fields with projects with a low net present value (NPV). The objective of this work was to study the technical-economical best option to develop an oil field in the Brazilian Northeast using reservoir simulation. Real geology, reservoir and production data was used to build the geological and simulation model. Due to not having PVT analysis, distillation method test data known as the true boiling points (TBP) were used to create a fluids model generating the PVT data. After execution of the history match, four development scenarios were simulated: the extrapolation of production without new investments, the conversion of a producing well for immiscible gas injection, the drilling of a vertical well and the drilling of a horizontal well. As a result, from the financial point of view, the gas injection is the alternative with lower added value, but it may be viable if there are environmental or regulatory restrictions to flaring or venting the produced gas into the atmosphere from this field or neighboring accumulations. The recovery factor achieved with the drilling of vertical and horizontal wells is similar, but the horizontal well is a project of production acceleration; therefore, the present incremental cumulative production with a minimum rate of company's attractiveness is higher. Depending on the crude oil Brent price and the drilling cost, this option can be technically and financially viable.

Modelagem matemática e experimental da perda de injetividade em poços canhoneados

Water injection in oil reservoirs is a recovery technique widely used for oil recovery. However, the injected water contains suspended particles that can be trapped, causing formation damage and injectivity decline. In such cases, it is necessary to stimulate the damaged formation looking forward to restore the injectivity of the injection wells. Injectivity decline causes a major negative impact to the economy of oil production, which is why, it is important to foresee the injectivity behavior for a good waterflooding management project. Mathematical models for injectivity losses allow studying the effect of the injected water quality, also the well and formation characteristics. Therefore, a mathematical model of injectivity losses for perforated injection wells was developed. The scientific novelty of this work relates to the modeling and prediction of injectivity decline in perforated injection wells, considering deep filtration and the formation of external cake in spheroidal perforations. The classic modeling for deep filtration was rewritten using spheroidal coordinates. The solution to the concentration of suspended particles was obtained analytically and the concentration of the retained particles, which cause formation damage, was solved numerically. The acquisition of the solution to impedance assumed a constant injection rate and the modified Darcy´s Law, defined as being the inverse of the normalized injectivity by the inverse of the initial injectivity. Finally, classic linear flow injectivity tests were performed within Berea sandstone samples, and within perforated samples. The parameters of the model, filtration and formation damage coefficients, obtained from the data, were used to verify the proposed modeling. The simulations showed a good fit to the experimental data, it was observed that the ratio between the particle size and pore has a large influence on the behavior of injectivity decline.

Utilização da cinza da casca de arroz em cimentação de poços de petróleo

Pozzolanic materials such as rice husk ash are widely used to substitute part of cement, because they react with calcium hydroxide (CH) producing calcium silicate hydrate (C-S-H), which aggregate better physical, chemical and mechanical properties to the cement slurry. The usage of rice husk biomass ash from agribusiness in addition to or partially replacing cement is a noble purpose and a good way of sustainable development which currently is an obsession around the world. The ashes utilized in this study were characterized by: scanning electron microscopy technique (SEM), Fourier transform infrared spectroscopy (FTIR), Energy-dispersive X-ray spectroscopy (EDX) and BET method. The pozzolanic activity of RHA and WRHA in cement slurries was evaluated by: thermal-gravimetric technique and derivative thermogravimetry (TGA/DTG), X-ray diffraction (XRD) and Compressive Strength. The slurries formulated with additions of 10% and 20% of RHA and WRHA were cured for 28 days at 58 °C. The results of thermal analysis demonstrated that a 20% WRHA addition caused a reduction of approximately 73% of Portlandite (calcium hydroxide – CH) phase related to standard slurry (STD). The XRD scans also demonstrated the reduction of the Portlandite peaks’ intensity for each slurry compared with STD slurry. The RHA and WRHA react chemically with Portlandite producing calcium silicate hydrate (C-S-H), confirming their effect as a pozzolanic agent. The WRHA presented the best results as a pozzolanic material.

Análise comparativa de diferentes configurações de poços no processo de combustão in-situ

With an increasing number of mature fields, heavy oil recovery has performed one of the great challenges of the oil industry. The Brazilian Northeast, for example, has numerous heavy oil reservoirs are explored with the use of thermal methods. Among the types of methods used for heavy oil, there is the method of in-situ combustion, a technique in which heat is produced within the container, unlike the injection of heated fluid when the heat is generated at the surface and transported to the reservoir. In this type of process, it is common to use vertical wells as injectors and producers. However, methods which use horizontal wells like oil producers are increasingly studied because of greater contact area between the formation and combustion front. Thus, the main objective of this work was to study the different configurations of wells (CIS THAITM and CAGD) in the process of in-situ combustion in oil recovery using a semi-synthetic tank with Brazilian Northeast features. The method "toe-to-heel air injection" (THAITM) is a process of enhanced oil recovery, which is the integration of in-situ combustion with technological advances in drilling horizontal wells. This method uses horizontal wells such as oil producers, keeping vertical injection wells for injecting air. The oil drain process by differential gravitational assisted with combustion (CAGD) is an integrated, in this configuration the horizontal injector well is drilled at the top formation with a horizontal production well in the lower section. The simulations were performed in a commercial program of thermal processes, called "STARS" (Steam, Thermal, and Advanced Processes Reservoir Simulator), the company CMG (Computer Modelling Group). An analysis of the air flow injection was performed and it was found that each method had a maximum injection to the base model, a show that through this air injection limit was reduced cumulative production of oil. Analyses of operating parameters were used: injection flow, configuration and completion of wells. In the sensitivity analysis we found that the air injection flow showed greater influence on THAI method, since the CIS method the completion of the wells was the most influential parameter and CAGD configuration wells showed the greatest influence in the recovered fraction. The economic results have shown that the best case obtained in CAGD method because, despite having higher initial cost showed the best financial return compared to the best cases the CIS and THAI.

Análise comparativa de diferentes configurações de poços no processo de combustão in-situ

With an increasing number of mature fields, heavy oil recovery has performed one of the great challenges of the oil industry. The Brazilian Northeast, for example, has numerous heavy oil reservoirs are explored with the use of thermal methods. Among the types of methods used for heavy oil, there is the method of in-situ combustion, a technique in which heat is produced within the container, unlike the injection of heated fluid when the heat is generated at the surface and transported to the reservoir. In this type of process, it is common to use vertical wells as injectors and producers. However, methods which use horizontal wells like oil producers are increasingly studied because of greater contact area between the formation and combustion front. Thus, the main objective of this work was to study the different configurations of wells (CIS THAITM and CAGD) in the process of in-situ combustion in oil recovery using a semi-synthetic tank with Brazilian Northeast features. The method "toe-to-heel air injection" (THAITM) is a process of enhanced oil recovery, which is the integration of in-situ combustion with technological advances in drilling horizontal wells. This method uses horizontal wells such as oil producers, keeping vertical injection wells for injecting air. The oil drain process by differential gravitational assisted with combustion (CAGD) is an integrated, in this configuration the horizontal injector well is drilled at the top formation with a horizontal production well in the lower section. The simulations were performed in a commercial program of thermal processes, called "STARS" (Steam, Thermal, and Advanced Processes Reservoir Simulator), the company CMG (Computer Modelling Group). An analysis of the air flow injection was performed and it was found that each method had a maximum injection to the base model, a show that through this air injection limit was reduced cumulative production of oil. Analyses of operating parameters were used: injection flow, configuration and completion of wells. In the sensitivity analysis we found that the air injection flow showed greater influence on THAI method, since the CIS method the completion of the wells was the most influential parameter and CAGD configuration wells showed the greatest influence in the recovered fraction. The economic results have shown that the best case obtained in CAGD method because, despite having higher initial cost showed the best financial return compared to the best cases the CIS and THAI.

Influência do tempo de adição do policarboxilato em pastas de cimento Portland para cimentação de poços petrolíferos

Cement pastes used in cementing oil wells operations are prepared according to the specific characteristics of each well. The physical properties requested for each folder formulation depend on the temperature and pressure of the well to be cemented. The rheological properties of the pulp are important control parameter for efficiency in transportation and positioning the folder during the cementing operation. One of the main types of additive used for the adjustment of rheological properties of cement pastes is the dispersant additive. This work aims to study the influence of variation of the time of addition of the polycarboxylate (0, 5, 10 and 15 minutes) in cement pastes, considering the initial periods of hydration of cement particles as fundamental point for better performance dispersant additive. Pastes were prepared with a density set at 15.6 lb/gal (1.87 g/cm3) and polycarboxylate concentrations ranging from 0.01 gpc to 0.05 gpc circulation temperature (BHCT) of 51°C and static temperature (BHST) of 76 C. The pastes were characterized from a rheological measurements, volume filtered, thickening time and resistance to compression formulations. Also were carried out tests Diffraction X-ray (XRD) and Scanning Electron Microscopy (MEV). The results showed that the addition of policaboxilato after 15 minutes decreased by 70% the values of rheological parameters. According to results of DRX and MEV, the addition of dispersant after 15 minutes did not affect the chemical reactions and subsequent formation of cement hydration products. A study of the economic feasibility to realize the financial benefits of the technique, which can be seen only with the use of the technique in this work to reduce the cost of production of cement paste was carried out, can get up to $ 1015.00 for each folder 100 barrels produced with said formulations.