IBP1779_12 FORMATION FLUID SAMPLING WITH DRILLING FLUIDS TRACERS, AND DOWNHOLE MONITORING: NEW PROCESSES Correa J.

1, Wander A. 2, Caas J. 3 , Barroso A.4, Rodrigues, E.5, Ortiz R.6, Colacelli S.7

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings.

Abstract
Reservoir fluid sampling is important for reservoir characterization and management. When sampling formation water or hydrocarbons with wireline formation testers (WFT) in wells drilled with WBM and SBM respectively, it is important to track mud filtrate contamination by distinguishing between formation fluid and mud filtrate. Current techniques for water sampling are mainly qualitative, either readings by stations or require coloring the mud and could be affected by temperature. While for hydrocarbon sampling a wider set of downhole fluid analyzers exist to address the more complex nature of the reservoir hydrocarbons. We present a solution that allows continuous monitoring of the formation fluid sampling cleanup process using a fluorescent tracer added to the mud systems while drilling the zone of interest by means of a downhole fluorescence sensor of a WFT string. Prejob calibrations allowed us to interpret the fluorescence sensors reading, considering that the formation water is free of fluorescence response and any response will indicate the presence of filtrate in the flowing fluid. For the hydrocarbons sampling, since the formation hydrocarbons have components with natural fluorescence, the tracer solution is applicable but the tracer needs to have a clearly different fluorescence response compared to the formation fluids to indicate the presence of filtrate or by using the fluorescence of the reservoir hydrocarbon when it is well distinguished from the SBM filtrate fluorescence response. The fluorescent tracers identified for these processes were found appropriate for this task because they are detectable at very low concentrations during qualification tests. Additionally, no tracer absorption issues were detected in the reservoir or pressure and temperature limitations on the cases studied. Field examples compared with laboratory results that confirm the success of this real-time monitoring solution are presented for heterogeneous offshore conditions. Complimentary, best practices for selection of sampling stations and formation testers were improved.

1. Introduction
Reservoir fluid sampling is very important for reservoir characterization, evaluation and management. The importance of high quality fluid data in the early stages of a reservoir is widely recognized. In that way, fluid data is essential for reservoir evaluation and development, including field development plans, facilities design, well completion and asset management among other aspects (Mullins and Schroer 2000; Betancourt et al. 2004, Lawrence et al. 2008). Consequently, fluid sampling validity/quality of both hydrocarbon and water is a main issue for reservoir characterization particularly at the exploration stage when fluids are closest to their original conditions. Thus, representative downhole fluid samples (hydrocarbon and water) of the formation of interest should be free of any contamination by drilling fluids (Betancourt et al. 2004; Correa et al. 2011).

______________________________ 1 Geologist - OGX 2 Geologist - OGX 3 Master, Petroleum Engineering - SCHLUMBERGER 4 Master, Petroleum Engineering MI-SWACO 5 Chemical Engineer MI-SWACO 6 Master, Petroleum Engineering - SCHLUMBERGER 7 Electronic Engineer SCHLUMBERGER

Rio Oil & Gas Expo and Conference 2012 Valid reservoir fluid samples must satisfy two important conditions: first, a minimum amount of contamination from mud filtrate should be present in the sample especially when they are miscible; and second, sample should be obtained under conditions that guarantee a single phase (Betancourt et al. 2004). Hydrocarbon samples are important to understand its properties, determine phase behavior and the presence of components such as asphaltenes, wax and gas that are essential to understand reservoir architecture and to prepare field development plans (FDP). Optimal production strategies, effective development decisions, assessment of reserves and economic values, flow assurance among other are some of the main incentives for collecting representative hydrocarbon samples. Analysis of formation water can provide crucial input to analyses during every stage in the life of a reservoir (Abdou et al. 2011). It provides information about the scaling and corrosion potential of the water, establishes the salinity of the water for petrophysical evaluation, and helps evaluate reservoir connectivity. It is a critical input to field development planning and economics. Sample quality depends strongly on drilling-fluid type and on sampling technique and monitoring. When filtrate and reservoir fluids are immiscible (WBM in an oil reservoir or SBM in a water reservoir), good samples are normally obtained because the mud filtrate, being immiscible with the reservoir fluid, does not contaminate the reservoir fluid sample (Schroer et al. 2000, Lawrence et al. 2008). In contrast, when the mud filtrate is miscible with formation fluids (WBM in a water reservoir or SBM in a hydrocarbon reservoir), it can cause chemical reactions and mixing that can contaminate the reservoir fluid samples. For example, a WBM containing sulfates in contact with a formation water containing barium could cause precipitation of barium from the water sample. Analysis of the resulting water sample would underestimate barium content and thus underestimate scaling potential of the formation water (Raghuraman, OKeefe et al. 2005). Similarly, the SBM filtrate is miscible with the oil; in consequence oil samples captured will contain the reservoir fluid with added filtrate (Mullins and Schroer 2000, Gozalpour et al. 2005). The impact of SBM contamination is severe as it can produce drastic changes in the nature of the fluid and its properties, especially for volatile hydrocarbons (Betancourt et al. 2004, Lawrence et al. 2008). Reservoir fluid samples are usually collected with a wireline formation tester, comprising a probe or packer module, pumpout module, fluid analyzer and sample-collection chambers. Fluids are drawn from the reservoir into a flowline in the device, in which different properties such as resistivity, optical properties, density and viscosity are measured. Early in the sampling process, fluid content is dominated by drilling-mud filtrate. With continued flow, contamination by drilling fluids decreases. Traditionally the real-time monitoring is performed either by using a resistivity sensor in a qualitative way (WBM) or optical fluid analyzers in a quantitative way to detect when the formation fluid is free of mud contamination (SBM). During this cleanup phase, the contaminated fluids are discharged into the borehole through the exit port. Formation fluid is collected in the sample chambers only after meeting stipulated criteria, thus ensuring sample quality. In the case of WBM environments, real-time contamination monitoring can be performed by measuring resistivity. This works well if there is a sufficient resistivity contrast between the WBM filtrate and formation water, but it is usually a qualitative process. Tracers are sometimes added to drilling fluids to allow calculation of the residual filtrate contamination in collected samples by subsequent laboratory analysis or in case of water-soluble colored tracer dye, the clean up can be monitored employing a downhole spectrometer to monitor the cleanup process (Hodder et al. 2004), however they can be affected by scattering and temperature. A more recent development for monitoring water sampling in real-time is pH measurement of formation water at reservoir conditions (Raghuraman, Xian et al. 2005; Carnegie et al. 2005). The downhole pH measurement technique injects pulses of pH-sensitive dyes into the flowline of a wireline formation tester while the formation sample is flowing. These pH-sensitive dyes are different from the originally pH-insensitive tracer dye that is added directly to WBM to track contamination. The pH-sensitive dyes change color according to the pH of the fluid in the flowline. The color change is detected at the appropriate wavelengths by an optical fluid analyzer. The pH of WBMs and filtrates is typically much higher (7 to 10 units) than that of formation waters (5 to 6.5 units); hence, pH can be used to differentiate between the two. The variation in pH with sampling time broadly follows the trend of the resistivity sensor and can be used for contamination monitoring in SBM and WBM environments. Once the level of contamination in the flowline fluid is low enough for good quality, water samples are collected. In the case of hydrocarbon samples in SBM environments, contamination can be estimated and monitored by measuring the optical properties of the filtrate and crude oils (Mullins and Schroer 2000, Betancourt et al. 2004, Lawrence et al. 2008) by means of a downhole fluid analyzer tool. The monitoring of fluid color and methane concentration (or GOR) has been used successfully to estimate in real time the amount of contamination fluid (Mullins and Schroer, 2000, Doeng et al. 2002, Betancourt et al. 2004). Normally, filtrate has less coloration than crude and do not contain methane (Mullins and Schroer, 2000). Analysis of the variation in coloration and the methane content with time can be monitored to assess the reduction of SBM filtrate contamination. When an acceptable value of the contamination in the sample is reached, the contamination is considered low and samples are collected. However these processes can be affected by scattering of the signal, presence of emulsions and the presence of large concentrations of water, among other effects. 2

Rio Oil & Gas Expo and Conference 2012 Considering some of the limitations in the existing sampling contamination monitoring techniques such as cases with small resistivity contrast between the WBM filtrate and formation waters, qualitative interpretation of the resistivity and pH sensors measurements, and limitations of the color dye tracers (cost and limited availability), scattering in the absorption channels from particulates in the flow line compromising the process, presence of emulsions in the case of SBM, the presence of large concentrations of water among other effects, a solution was implemented that allows continuous monitoring of the reservoir sampling cleanup process as a way to better understand cleanup profiles without altering the normal mud appearance or altering the formation characteristics. To achieve this goal, a fluorescent tracer was added to the mud system while drilling the zone of interest. By adding this tracer, we were able to continuously monitor the cleanup process by means of the downhole fluorescence sensor of a wireline formation tester (WFT) string, starting from the principle that fluorescence measurements are still sensitive to even small concentrations of flurophores in the fluid and are less affected. Prejob calibrations allowed us to interpret the fluorescence sensors reading, considering that the formation water is free of fluorescence response and that any response will indirectly indicate the presence of filtrate in the flowing fluid for the WBM case. For the hydrocarbons sampling, considering that the formation hydrocarbons have fluorophres, components with natural fluorescence response, the previous solution is applicable but the tracer needs to have a clearly different fluorescence response compared to the formation fluids to indicate the presence of filtrate in the flowing fluid or by using the fluorescence of the reservoir hydrocarbon when it is well distinguished from the SBM filtrate fluorescence response. The fluorescent dyes were found appropriate to these tasks because they are detectable at very low concentration levels during qualification tests performed at surface conditions. Additionally, there were no detected tracer absorption issues in the reservoir affecting the process or pressure and temperature effects for the studied cases. In this paper, we first explore the factors that affect the fluorescent dye values of mixtures when two different fluids are combined. Next, we study fluorescent dye sensitivity to contamination in carbonate reservoirs and WBM and SBM filtrate environments. Finally, we present the successful results from field tests in which these concepts have been applied.

2. Theory of Downhole Fluid Analysis Measurements

2.1. Optical Measurements. Downhole Fluid Analysis (DFA) technology is a concept, rather than a specific tool. Current DFA technology use absorption spectroscopy of reservoir fluids in the visible-to-near-infrared (VIS/NIR) range (Betancourt et al. 2004, Dong et al. 2007). These measurements are widely used today as the primary method to investigate reservoir fluids under downhole conditions by a wireline formation tester. In-situ fluid analysis, which began as a means to assure quality control during fluid sampling, has evolved into a key technique for characterizing the distribution of reservoir fluid properties and for determining zonal connectivity across a reservoir. VIS/NIR spectroscopic measurements coupled with reflection and fluorescence measurement have evolved to the degree that it is possible to measure oil/water/gas fraction; to derive hydrocarbon composition (C1, C2, C3-C5, C6+), and carbon dioxide (CO2) from the formation fluid spectra obtained in real time; to measure gas-to-oil ratio (GOR); to provide a fluorescence measurement and a pH measurement; and, from the difference in absorption spectrum between reservoir fluid and filtrate of SBM or WBM, to assess fluid sample contamination from the drilling fluid. (Schroer et al. 2000; Mullins, Daigle et al. 2001, Fujisawa, van Ahthoven et al. 2002, Fusijawa, Mullins et al. 2003, Betancourt et al. 2004, Hodder et al. 2004, Mullins, Hashen et al. 2004, Carnegie et al. 2005; Raghuraman, OKeefe et al. 2005; Raghuraman, Xian et al. 2005; Abdou et al. 2011). 2.2. Fluorescence Measurements The fundamentals principles of fluorescence spectroscopy are related to those for light absorption (Betancourt et al. 2004). Fluorescence data can provide insight into the dynamics of various processes after the deposition of electronic excitation energy (Turro 1978). In addition to contributing to fundamental understanding, fluorescence methods are useful in diverse applications, such as those involving crude oils (Tissot and Welte 1984). For instance, in the petroleum industry, fluorescence is routinely employed during drilling as an indicator of the presence of crude oil in drilling cuttings (DeLaune 1992; Reyes 1993). Almost all crude oils fluoresce because they contain aromatic components. The molecules that are responsible for UV-visible fluorescence in crude oils are the polycyclic aromatic hydrocarbons (PAH). The aborption of electromagnetic energy applied to an aromatic ring disturbs its internal electron structure creating an excited state that, during relaxation, can lead to the emission of radiant energy in the form of light called fluorescence after a discrete amount of time (in the order of nanoseconds) (Reyes 1993; Betancourt et al. 2004). These molecules not only fluoresce, but are also responsible for the coloration of the fluid (light absorption is necessary for light emission). The fluorescence spectrum for excitation at 470 nm of different hydrocarbons is shown in Figure 1 3

Rio Oil & Gas Expo and Conference 2012 (Betancourt et al. 2004). Also, for some natural materials related to crude oils, high fluorophore concentrations produced spectral red shifts and intensity reduction of fluorescence (Durand 1980). These observations are used to help gauge the evolution of these natural materials. Recently, fluorescence lifetimes of several crude oils have been measured to evaluate molecular size and weight of asphaltene and asphaltene solubility fractions (Mullins, 2005; Badre et al. 2006).

Figure 1. Fluoresce Spectrum of different hydrocarbons. Variation is observed is observed in fluorescence intensity and spectra among different crude oils presented from lightest to the heaviest (Betancourt et al. 2004) 2.3. Fluorescence to estimate Mud Contamination Measurements. An alternative approach for mud contamination measurement is to use a fluorescent dye and a downhole fluorescence detection sensor. The authors wish to stress the monitoring of this measurement at downhole conditions in real time. At the time of writing this article and to the best knowledge, all work around this topic has been done at surface conditions. Recently, fluid contamination in rock core and brine samples intended for microbiological monitoring at a CO2 storage site was performed using fluorescent dye tracers; however samples contamination analysis was performed only at the lab (Wandrey et al. 2009). The authors present a solution that allows continuous monitoring of the formation fluid sampling cleanup process as a way to better understand cleanup profiles. To achieve this goal, a fluorescent tracer was added to the mud system while drilling the zone of interest. By adding this tracer, we were able to continuously monitor the cleanup process by means of the downhole fluorescence sensor of a wireline formation tester (WFT) string. Prejob calibrations allowed us to interpret the fluorescence sensors reading, considering that the formation water is free of fluorescence response and that any response will indicate the presence of filtrate in the flowing fluid for the WBM case. For the hydrocarbons sampling, considering that the formation hydrocarbons have fluorophres, components with natural fluorescence response, the previous solution is applicable but the tracer needs to have a clearly different fluorescence response compared to the formation fluids to indicate the presence of filtrate in the flowing fluid. For the present cases the fluorescent dyes identified for these processes were found appropriate for the sample contamination analysis because they are detectable at very low concentration levels (to ~ 1ppm), during qualification tests performed at surface conditions, are insensitive to pH and have a fluorescence emission peak at the correct energy for the proper downhole detection. Additionally, there were no detected tracer absorption issues in the reservoir affecting the process and not pressure or temperature limitations were observed for the studied cases. Another advantage is that the fluorescent dye has a high quantum yield and is fairly valued and readily available. The downhole fluorescence detection sensor employs a geometry in which the depth of investigation is short so the measurement is less affected by scattering. Figure 2 shows a simplified scheme of the downhole fluorescence detector. It has one excitation light, one reflection measurement channel, and two fluorescence detection channels. Fluorescent material as crude oil or substances containing fluorophores absorbs the excitation light energy and then emits the fluorescence light. The fluorescence light from the fluorophores can be detected with two detection channels. As only the crude oil or fluorophore substances give us a fluorescence light, and WBM / SBM filtrates emit little or no fluorescence, a fluorescence detector should be good to discriminate crude oil from SBM filtrate if the filtrate has a clear different fluorescence response and formation water from WBM filtrate with fluorophores tracers. However hydrocarbons with high asphaltene concentration undergo collisional quenching phenomena leading to fluorescence damping (Canas et al. 2007), making it difficult to differentiate from the SBM fluorescence. The uses of tracers in the SBM mud can provide a better differentiation (different fluorescence response) between the reservoir fluids and drilling fluids to indicate the presence of filtrate in the flowing fluid. The cases for natural hydrocarbon has been already presented for the case of crude oils and WBM filtrate in the literature (Mullins 2005; Badre et al. 2006; Correa et al. 2011) and is reported for the first time in the case of SBM filtrate in this article. 4

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Figure 2. Downhole fluoresce detector Schematic

3. Laboratory Tests
3.1. WBM filtrate lab results The tracer interference on formation cuttings fluorescence analysis was evaluated in order to guarantee hydrocarbon characterization at shaker cuttings sample. Two scenarios were considered; one with the basic WBM drilling fluid without tracer and another with WBM tracer. Filtration and solids simulating cuttings were immersed in these two types of fluids for evaluation. The filter cake and solids resulting from comparative tests were analyzed in a fluoroscope and did not present significant additional fluorescence. In this sense the tracer interference should not be considered as an issue into the perspective of formation cuttings analysis. Additionally, a field test was run mixing the WBM tracer at standard concentration with the fluid in a non reservoir phase and no fluorescence was detected by field geologists, evidencing again the lack of interference on the cutting as desired. Figure 3(a) and Figure 3(b) shows filter cake pictures comparing results with and without tracer mixed in the fluid. (a) (b)

Figure 3. (a) Filter cake from WBM filtration without tracer (left) and with tracer (right) before rolling (b) Filter cake from WBM filtration without tracer (left) and with tracer (right) after rolling Figure 4(a) shows laboratory tests of water samples with the selected fluorescent tracer illuminated by visible light and Figure 4(b) shows the tests with UV light (right). With the UV illumination, fluorescence is observed (strong green color). Figure 5(a) shows the laboratory tests with a wireline downhole fluorescence sensor performed at surface conditions using water samples from one of the studied formations, fresh and industrial water, and the typical WBM filtrate in the studied area, with the addition of the selected fluorescent tracer. The light green color emission of the fluorescence light in the WBM filtrate containing fluorophores tracers is clear. Figure 5(b) shows the fluorescent tracer concentration versus the detected fluorescence signal for the case of WBM using a wireline downhole fluorescence sensor which has a 470-nm excitation source in combination with a 550nm long pass filter that allows picking up fractions of the total fluorescent emission with accuracy. A linear fit of the primary absorption peak at 550 nm with R2 values at 98% is observed. The tested fluorescent tracer has a high quantum yield that is detectable at low concentration levels (to ~ 1 ppm). However, the tests suggest that for field implementation the concentration should be between 40 and 100 ppm in the WBM filtrate. 5

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Figure4 (a) Water and base oil samples illuminated by visible light and (b) UV light. With the UV illumination, fluorescence is observed in the water phase containing the fluorescent tracer (green color). (a)

(b)

Figure 5. (a) Samples of water without and with fluorescent tracer under UV illumination. Fluorescence is observed. (b) Fluorescent tracer concentrations versus detected fluorescence signal showing a linear fit of primary absorption peak at 550 nm with R2 values at 98%. 3.2. SBM filtrate lab results Laboratoty tests shows that the studied SBM tracer may present light interference on some formation cutting (matterial) but it is easy to be differentiated from reservoir hydrocarbon by specialist in the fluoroscope techniques, results are presented in Figure 6(a). Figure 6(b) shows fluoroscope laboratory test results of native oil, SBM filtrate with tracer and SBM filtrate itself. From the figure a clear difference response in fluorescence is noticed.

Figure 6. (a) Top shows bentonite recovered from the SBM with tracer. Bottom shows bentonite recovered from SBM contaminated with Oil. (b) Fluoroscope image of native oil, SBM with tracer and SBM filtrate Figure 7(a) shows the results for the fluorescence tracer concentration versus the detected fluorescence signal for the case of SBM using a wireline downhole fluorescence sensor as was done with the WBM. The normalized results for Fluoresence Channel (FLDO) and Fluorescence Ratio (FLRA) showed in Figure 7(b) have a logical behavior 6

Rio Oil & Gas Expo and Conference 2012 showing a tendency that could allow defining a practical method for computing contamination in real time, presenting better contrast than the current methodologies and eventually could allow a more approachable way to compare results between sampling stations and/or wells.

Figure 7. (a) Fluorescent tracer concentrations versus detected fluorescence signal for crude oil and SBM contamination using fluorescence tracers. (b) Normalized response for sensors readings

4. Field Tests
After the laboratory tests, field jobs were performed, and the results from two field cases in heterogeneous offshore conditions for the WBM case and the results for a field case with SBM having a clear different response from the natural hydrocarbon fluid are presented in the following paragraphs. Table 1 summarizes the fluid sample contamination results from the real-time analysis using fluorescence readings and the later laboratory analysis for the WBM cases confirming the success of this reail-time monitoring solution. Table 1. Comparison between contamination calculated by fluorescence computation in real time and the laboratory analysis for samples in flied cases Field Case 1 1 2 3 4.1. WBM filtrate Case 1 For the selected well, the target formation was drilled with the fluorescent tracer at doses of 70 ppm in the WBM drilling fluid. Mud and filtrate samples were collected from the fluid stream going into and out of the wellbore every 50 m drilled to count with a detailed fluid database for further analysis and evaluation. The response of the downhole fluid sensor was confirmed using WBM filtrate samples prepared with different fluorescence tracer dilutions. The resulting calibration plot is presented in Figure 8 and it was used as the base for the real-time WBM filtrate contamination monitoring. Station 1 2 1 2 Contamination, % Real Time Analysis 1 2 4 8 Contamination, % Laboratory Analysis <1 <2 6 3.6

Figure 8. Fluorescent tracer concentrations versus detected fluorescence signal for Case 1 (FLDO: Fluorescence Reading). 7

Rio Oil & Gas Expo and Conference 2012 Figure 9 (a, b) shows the two formation water sampling stations performed for Case 1. The locations of the wireline formation tester probe are presented together with the gamma ray (GR) and nuclear magnetic resonance (NMR) permeability indicator logs, and the real-time contamination monitoring results are shown Figure 9 (c, d). Fig. 10 (a, b) presents the real-time monitoring of the pumpout parameters (e.g., flow rate) with the continuous fluid resistivity and fluorescence readings from the downhole fluid analyzer sensors. Although the fluid resistivity profile is clean and reflects the cleanout process, the fluorescence readings present a better sensitivity profile and allow direct contamination quantification, as presented in Figure 10 (c, d). Additionally, Figure 11 (a, b) presents the downhole sensor fluorescence response together with the optical density fluid identification. The computed contamination results for Case 1 using the fluorescence data that are shown on Figure 11 (c, d) agree well with the laboratory analysis, the correspnded results are presented in Table 1.

Figure 9. Stations 1 and 2 for Case 1. (a, b), locations of the formation tester probe and GR and NMR logs. (c,d) realtime contamination monitoring results using the fluid fluorescence response (DDM: station drawdown mobility). Figure 9 (a, b) shows the two formation water sampling stations performed for Case 1. The locations of the wireline formation tester probe are presented together with the gamma ray (GR) and nuclear magnetic resonance (NMR) permeability indicator logs, and the real-time contamination monitoring results are shown Figure 9 (c, d). Figure 10 (a, b) presents the real-time monitoring of the pumpout parameters (e.g., flow rate) with the continuous fluid resistivity and fluorescence readings from the downhole fluid analyzer sensors. Although the fluid resistivity profile is clean and reflects the cleanout process, the fluorescence readings present a better sensitivity profile and allow direct real time contamination quantification, as presented in Figure 10 (c, d). The computed contamination results for Case 1 using the fluorescence agree well with the laboratory analysis as presented in Table 1. Besides the fluid sampling monitoring and contamination evaluation in real time, this experience helps to optimize the station selection for downhole formation fluid sampling using formation testers considering the reservoir heterogeneity, wellbore drilling parameters, and formation testers capabilities. In the present case, it was seen that stations at the bottom of the formation layer, mainly if thick packages were tested, were detrimental for the operation time because of the high degree of segregation of the drilling fluid filtrate inside the formation. 4.2. WBM filtrate Case 2 For the selected well, the target formation was drilled with the fluorescent tracer at doses less than 10 ppm in the WBM drilling fluid. Figure 11(a) shows the pumpout parameters including flow rate, pressure, temperature, resistivity, and fluorescence response for the fluid sampling station in this well section. In this case, it is observed the marked noise response of the downhole fluid resistivity sensor does not allow for clear fluid-cleanout monitoring, while 8

Rio Oil & Gas Expo and Conference 2012 the fluorescence response presents a cleaner response for the analysis. Figure 11(b) shows the contamination monitoring results obtained using the fluorescence response.

Figure 10. Stations 1 and 2 for Case 1. (a,b) pumpout parameters including resistivity and fluorescence response. (c, d) Bottom, contamination monitoring results using the fluid fluorescence response.

Figure 11. Station for Case 2. (a) pumpout parameters including flow rate, pressure, temperature, resistivity, and fluorescence response. (b) the contamination monitoring results using the fluid fluorescence response Figure 12 shows that in spite of the low concentration of fluorescent tracer used in this case (less than 10 ppm), it is still possible to monitor the fluid cleanout process considering the high resolution of the available downhole fluid analyzers to monitor the fluorescence response. Figure 12 also presents the contamination monitoring results using the fluid fluorescence response. Results agree reasonably well with the laboratory analysis as indicated in Table 1. 9

Rio Oil & Gas Expo and Conference 2012 However, for better accuracy, comparable to Case 1 (see Table 1), we suggest using fluorescent concentrations between 40 and 100 ppm in the WBM filtrate.

Figure 12. Station for Case 2. Downhole sensor fluorescence response and optical density fluid identification. 4.3. SBM filtrate Case 3 Figure 13 shows the results from the DFA tool for an oil well drilled with SBM. Figure 13(a) shows the GOR results, Figure 13(b) shows the real time (RT) interpreted composition, C1, C2, C3-C5, C6+ and CO2, Figure 13(c) shows the fluorescence response, Figure 13(d) shows the RT interpreted oil and water fractions and Figure 13(e) presents the RT fluorescence monitoring contamination results.

Figure 13. DFA tool measurements for a hydrocarbon station for Case 3. (a) GOR measurements, (b) Real Time (RT) interpreted composition, (c) fluorescence readings, (d) RT oil and water fraction, (e) RT contamination. 10

Rio Oil & Gas Expo and Conference 2012 As discussed before natural hydrocarbons contain fluorobores or fluorescence components that allow monitoring sampling clean out in SBM environments if the filtrate has a clear different fluorescent response. For this case it is clear from Figure 13(c) the differences in response fluorescence between the reservoir fluids and SBM filtrate. Using this principle to reinforce the sample contamination evaluation since the traditional methods to evaluate contamination were affected by the presence of free water from the reservoir and low optical density observed of the reservoir fluid, samples with low contamination were collected using a single probe and real time fluorescence monitoring as presented in Figure 13. The estimated contamination results for Case 3 agree well with the laboratory analysis. At the time of writing this article, final recommendations to select a candidate well to perform a field case with the selected tracer for SBM were undergoing to test and evaluate the proposed methodology. However based on the promissory results from the surface lab test and the example presented in case 3 the proposed methodology using fluorescence readings is the base for improved sampling contamination monitoring.

Conclusions
Field examples presented here clearly show the potential of fluorescence tracers as a real-time openhole logging measurement to characterize contamination at downhole conditions in real time. The ability of the tracer monitoring to differentiate in real time between WBM filtrate and formation water or SBM and formation oil helped to collect better formation fluid samples to optimize the reservoir characterization. This is of immense value in reserves estimation as well as in planning reservoir development strategies. In heterogeneous carbonate zones, conventional formation evaluation measurements such as openhole pressure and resistivity logs often fail to predict formation fluid types and the location of the oil/water contact because of large uncertainties associated with factors such as supercharging, capillary effects, complex and heterogeneous pore structures, wettability variations, and shoulder-bed effects. Downhole fluid analysis, which now includes the newly developed downhole fluorescence and pH measurements, offers a robust alternative for real-time formation evaluation and provides critical input for production planning and reservoir management. A novel real time monitoring downhole fluid analysis process was proposed for sampling formations hydrocarbons in SBM environments using the fluorescence in the native oils or adding tracers in the drilling mud when a larger fluorescence differentiation is required due the quenching of this phenomenon.

Acknowledgements
The authors wish to thank OGX Petroleo e Gas and Schlumberger for permission to publish results presented in the different case studies. The authors wish to thank all the colleagues who have contributed to this study.

References
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FUJISAWA, G., VAN AGTHOVEN, M.A., JENET, F., RABBITO, P., AND MULLINS, O.C.: Near-Infrared Compositional Analysis of Gas and Condensate Reservoir Fluids at Elevated Pressures and Temperatures, Applied Spectroscopy 56, 1615. 2002. FUJISAWA, G., MULLINS, O.C., DONG, C., CARNEGIE, A., BETANCOURT, S.S., TERABAYASHI, T., YOSHIDA, S., JARAMILLO, A.R., AND HAGGAG, M. Analyzing Reservoir Fluid Composition In-Situ in Real Time: Case Study in a Carbonate Reservoir, paper SPE 84092 presented at the 2003 SPE Annual Technical Conference and Exhibition, Denver, Colorado, 58 October. DOI: 10.2118/84092-MS. 2003. GOZALPOUR, F., DANESH, A., TODD, A.C., TOHIDI, B. Application of Tracers in Oil-Based Drilling Mud for Obtaining High Quality Reservoir Fluid Samples. Paper SPE 94067 presented at the SPE Europe/EAGE Annual Conference, Madrid, Spain, 1316 June, doi: 10.2118/94067-MS. 2005. HODDER, M.H., SAMIR, M., HOLM, G., AND SEGRET, G. Obtaining Formation Water Chemistry Using a Mud Tracer and Formation Tester in a North Sea Subsea Field Development. Paper SPE 88637, Perth, Australia, 1820 October. SPE-88637MS. doi: 10.2118/88637-MS. 2004. LAWRENCE, J.L., CHORNEYKO, D.M., SMITH, C.K., NAGARAJAN, N.R., Representative Reservoir Fluid Sampling: Challenges, Issues, and Solutions, paper IPTC 12402, Kuala Lumpur, Malasya, 3-5 December, 2008. MULLINS, O.C., SCHROER, J. Real-Time Determination of Filtrate Contamination During Open Hole Wireline Sampling by Optical Spectroscopy. Paper SPE 63071 presented at the SPE Annual Technical Conference and Exhibition, Dalla, Texas, 1-4 October, doi: 10.2118/63071-MS. 2000. MULLINS, O., DAIGLE, T., CROWELL, C., GROENZIN, H., AND JOSHI, N. Gas-Oil Ratio of Live Crude Oils Determined by Near-Infrared Spectroscopy, Applied Spectroscopy v. 55, n. 197. 2001. MULLINS, O.C., HASHEM, M., ELSHAHAWI, H., FUJISAWA, G., DONG, C., BETANCOURT, S., AND TERABAYASHI, T. Hydrocarbon Compositional Analysis In-Situ in Open hole Wireline Logging, paper FFF presented at the SPWLA 45th Annual Logging Symposium, Noordwijk, The Netherlands, June 69, 2004. MULLINS, O.C. Review of the Molecular Structure and Aggregation of Asphaltenes and Petroleomics. Paper SPE 95801 presented at the SPE Annual Technical Conference and Exhibition, Dallas, Texas, USA, 912 October. SPE-95801-MS. doi: 10.2118/95801-MS. 2005 RAGHURAMAN, B., OKEEFE, M., ERIKSEN, K.O., TAU, L.A., VIKANE, O.,GUSTAVSON, G, AND INDO, K. Real-Time Downhole pH Measurement Using Optical Spectroscopy. Paper SPE 93057 presented at the SPE International Symposium on Oilfield Chemistry, Houston, Texas, USA, 2-4 February. SPE-93057-MS. doi: 10.2118/93057-MS. 2005. RAGHURAMAN, B., XIAN, C., CARNEGIE, A., LECERF, B., STEWART, L.,GUSTAVSON, G., ABDOU, M.K., HOSANI, A., DAWOUD, A., EL MAHDI, A. AND RUEFER, S. Downhole pH Measurement for WBM Contamination Monitoring and Transition Zone Characterization. Paper SPE 95785 ATC, Dallas, Texas, USA, 912 October. SPE-95875-MS. doi: 10.2118/95785-MS. 2005. REYES, M. V. Application of Fluorescence Techniques for Mud Logging Analysis of Oil Drilled with Oil-Based Mud. SPE Formation Evaluation, v. 9, n. 4, p 300-305. DOI: 10.2118/25355-PA. 1994. SCHROER, J., MULLINS, O.C., AND BECK, G. Real-time Quantification of OBM Filtrate Contamination During Openhole Wireline Sampling by Optical Spectroscopy. Paper 2000-SS presented at the SPWLA 41st Annual Logging Symposium, Houston, Texas, USA. 2000. TISSOT, B.P. AND WELTE, D. H. Petroleum Formation and Occurrence. New York: Springer-Verlag. 1984 TURRO. N.J. Modern Molecular Photochemistry. Menlo Park, California: Benjamin/Cummings Publishing. 1978 WANDREY, M., MOROZOVA, D., ZETTLITZER, M., WUERDEMANN, H, AND THE CO2SINK GROUP. Assessingdrilling mud and technical fluid contamination in rock core and brine samples intended for microbiologicalmonitoring at the CO2 storage site in Ketzin using fluorescent dye tracers. International Journal of Greenhouse Gas Control, 4 (6): 972 980. doi:10.1016/j.ijggc.2010.05.012. 2010.

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