Organic Geochemistry

Organic Geochemistry 35 (2004) 15271536 www.elsevier.com/locate/orggeochem

Impact of modern deepwater drilling and testing uids on geochemical evaluations

Lloyd M. Wenger *, Cara L. Davis, Joseph M. Evensen, James R. Gormly, Paul J. Mankiewicz
ExxonMobil Upstream Research Company, P.O. Box 2189, Houston, TX 77252-2189, USA Received 6 October 2003; accepted 1 June 2004 (returned to author for revision 1 May 2004) Available online 15 September 2004

Abstract Evaluation of petroleum-uid properties, hydrocarbon shows, and source-rock characteristics requires new tools to properly recognize and correct for drilling and test-induced contamination, which is increasingly common in modern deepwater eld operations. Oil exploration, development, and now production, are more frequently conducted in deeper-water environments where the challenges faced by drilling and operations can severely impact the evaluation of oil and rock geochemistry and uid properties. Poorly consolidated sediments, swelling clay minerals, and responses to evolving environmental regulations regarding oshore disposal of drill cuttings have resulted in the widespread use of enhanced mineral oil or synthetic-based muds. Also, water-based drilling uids used in some deepwater operations contain additives that may impact uid and rock geochemistry. For example, asphalt-based shale stabilizers are added to aid well-bore competency and prevent sticking drill pipe, and polyalkylated glycols are added to depress freezing temperatures and prevent the formation of gas hydrates in the drilling mud. Because these and other additives are often a signicant component of water-based muds, they may aect the geochemical signature of uids and rocks and alter uid properties. Highly saline brines are another important source of contamination as they are used in completion uids, water-wet muds, and are emulsied in oil-wet muds. Brine components impact metal contents of petroleum-uid tests and complicate the determination of formation-water compositions. Despite potential problems introduced by these additives, successful strategies can be devised to accurately access key geochemical and engineering parameters. 2004 Elsevier Ltd. All rights reserved.

1. Introduction The high costs of drilling, production testing, and facilities construction in deepwater eld operations require that high-quality uid and rock data are acquired for appropriate economic decision-making. Specically,
Corresponding author. E-mail address: lloyd.m.wenger@exxonmobil.com (L.M. Wenger).
*

accurate uid properties to determine oil quality and value, and reservoir compartmentalization are critical to eld evaluation. When source rocks are penetrated, correct characterization of source type, richness and maturity are needed to constrain expected uid type and properties. However, the rapidly evolving technology necessitated by deepwater drilling and operations has resulted in a spectrum of new contaminants that need to be recognized and either removed prior to sample analysis or corrected for numerically.

0146-6380/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.orggeochem.2004.07.001

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Drilling muds and completion uids used in deepwater operations may complicate the interpretation of geochemical and engineering data. Both oil- and water-based muds may impact bulk hydrocarbon uid properties, geochemical signatures, and source rock properties. Highly saline aqueous uids, the dominant component of most completion uids and important components of both water-wet and oil-wet drilling muds, may contribute ionic species that contaminate oil and/or water phases. Accurate well-log analysis requires determination of uncontaminated formation-water salinity and composition. The prevalence of biodegraded hydrocarbon uids in many deepwater reservoirs has increased interest in naphthenic acid salts (metal naphthenates), which form through interaction of naphthenic acids from biodegraded oils and formation waters and can cause serious oil-quality and scaling problems. Consequently, it is important to recognize contamination eects in both oil and water phases. Representative formation uid samples are required to evaluate the viability of a discovery or relationship to nearby accumulations. Extent of uid-test contamination must be determined in order to correct measured uid properties such as API gravity and gas/oil ratio (GOR), particularly for wireline formation test (WFT) samples. Estimation of additional uid properties including total acid number (TAN), sulfur, vanadium and nickel contents, and gross compositions (e.g., asphaltene content) may also be important. An estimate of the formation uid composition is obtained by subtracting the drilling-uid gas-chromatographic signature, determined by analysis of the mud ltrate, from the contaminated-test signature. Because muds are often re-used, ltrates pressed from actual muds used in each well need to be obtained for reference analyses. This correction technique is calibrated by comparing the properties of uncontaminated drill-stem test (DST) oils with those for contaminated small-volume wireline samples taken from equivalent reservoir zones. Corrections for saturation pressure and live viscosity are less direct, requiring equation-of-state models. The geochemical evaluation of contaminated-uid tests and shows (e.g., from reservoir sidewall cores) requires a thorough knowledge of the signatures imparted by potential contaminants on all analyses (e.g., GCs, GC/MS). As drilling muds are re-used between wells, it is important to consider the history of the mud and to recognize changes made to the mud system during drilling. Records of the use of additives or changes during drilling are readily determined from drilling operations reports. The list of available additive types and manufacturer specications is extensive (see summary in World Oil June, 2003). The risk of encountering overpressure while drilling and the need to assure well control has led to a tendency to drill with over-balanced mud-weight systems which often lead to ushing of reservoir uids from the well-

bore vicinity. This can render conventional mud-log hydrocarbon-show evaluation more tenuous and possibly lead to by-passed pay. Although less commonly used in deepwater drilling, water-based mud systems can also signicantly impact geochemical evaluations. Extremely high salinity brines (to 300,000+ ppm total dissolved solids) are used to inhibit shale activity in water-wet mud systems and to prevent gas-hydrate formation. Gas hydrates can form in drilling mud under the low temperatures and high pressures encountered in the drill stem and tubulars in deepwater environments. Polyalkylated glycols are added to depress freezing point and inhibit their formation. Contamination in uid tests requires the development of correction calibrations to estimate the actual uid properties. Contamination of shale samples by polyalkylated glycols can be dicult to remove, presenting diculties for the evaluation of source rock potential. Additives based on sulfonated asphalt are also used to inhibit shale activity and promote well-bore stability. Targeted cleaning methods are required to accurately evaluate source-rock samples contaminated with these stabilizers. Following solvent removal of the polar contaminants, organic-richness is determined on solvent-cleaned rock samples and the non-polar extract fraction is characterized for source-rock properties and correlation. Deepwater drilling requirements have led to an increase in the brine salinity used in drilling muds, completion uids and during production tests. As a result of the prevalence of biodegraded oils in many deepwater environments, and the associated oil-quality and scale formation problems related to naphthenic acids and metal naphthenates, there is an increasing need to recognize real from contaminated signatures in uid tests. The rapidly evolving technology necessitated by deepwater operations has resulted in an increased and changing future role for petroleum geochemistry.

2. Drilling uid components From a geochemical standpoint, essentially all well samples received for analysis and interpretation have been in contact with drilling and/or completion uids that include additive contaminants. In order to properly evaluate the eects of these uids on measured properties, it is necessary to have a complete record of when and why these additives are introduced. Changes to the mud system and additive introduction during drilling are readily determined from drilling-operation reports. Because drilling muds are often re-used, additional forensic investigation may be required, such as which rig and well the mud was used for previously and the types and composition of hydrocarbons encountered. From the drilling or mud engineering viewpoint, all components of the mud system are present for a specic

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purpose. As shown in schematic diagram (Fig. 1), the inside of a drill pipe is lled with drilling mud, drill cuttings, and any encountered oil, gas, or formation water entering the mud system. The weighting solids (e.g., barite, hematite) are suspended in the continuous phase of the drilling mud, which is either oil- or water-based depending on the wettability requirements of the rock section being penetrated. The discontinuous phase of the mud system (e.g., brine droplets suspended in an oil-based system) must allow critical mud functions (e.g., suppression of swelling clay minerals) without impacting the desired wettability. Emulsiers allow the discontinuous phase to be incorporated into the continuous phase. Surfactants help maintain wettability during drilling.

Oil-Based Mud
Weight % (excluding weighting agents) : Activity Control
CaCl2

Alkalinity
Ca(OH)2

Emulsifiers
- Ca-fatty acid soaps

Diesel, EMO or Synthetic oil

Filtration Control
- asphalt/gilsonite - amine clay - amine lignite

Viscosifiers
- amine clay - di/trimer acids

3. Oil-based drilling uids: composition and component functions A brief discussion of the composition and engineering function of drilling and completion uid is required to better understand the basis for the use of the various constituents common to deepwater drilling muds and completion uid systems. Oil-based mud systems are widely used in many deepwater environments, particularly Tertiary delta systems where unconsolidated sediments and swelling clay minerals are common. Generalized distributions of components used in deepwater oil-based mud systems are illustrated in Fig. 2. Components are shown in wt%, excluding weighting agents such as barite. Oil-wet systems contain a mixture of an oil-base uid and an aqueous-brine uid in a ratio

Fig. 2. Generalized distributions of components in oil-wet drilling mud uids in wt%, excluding weighting agents. See text for engineering purpose of various additives.

of approximately 7525% (5%). Years ago, oil-based mud almost always referred to a diesel-cut base. Today, oshore oil bases consist of either enhanced mineral oil (EMO, a highly rened, low-aromatic content diesel), or synthetic oil (no aromatic content). The oil phase is dispersed within the aqueous-phase brine through the addition of an emulsier, typically a calcium fatty-acid soap. The brine in oshore oil-based muds is typically a highly saline calcium chloride solution (commonly 30 wt%). Sodium chloride is sometimes used in deepwater

Fig. 1. Schematic of a drill pipe interior, lled with drilling mud, drill cuttings being cleaned away from the bit, and oil, gas, or water from the formation. The mud system lubricates the drill bit and sweeps drill cuttings away. The continuous phase is composed of oil or water base. The discontinuous phase, otherwise immiscible, is emulsied for uniform distribution. The engineering purpose of various drilling uid additives are summarized in the text.

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oil-based mud systems, but is not as favorable as calcium chloride due to a lower aqueous solubility. Highly saline brines are particularly desirable in deepwater muds, as the high-ionic strength prevents excessive swelling of clay minerals (activity control). An alkaline pH is typically maintained in oil-based muds by addition of calcium hydroxide. The mud needs to remain alkaline to prevent corrosion of well strings and tubulars and to neutralize acidity introduced by any carbon dioxide or hydrogen sulde that is encountered. Additional oil-based mud components include additives targeted at ltration control (maintenance of well-bore mud cake and prevention of drilling uid losses into the formation) and mud rheology (e.g., viscosity, yield point, gel strength). These additives include natural asphalts and gilsonites and specialized amine clay or amine lignite products.

nC16
(a)

nC12

Oil-Based (Diesel)
Pr

64.5% Sats 28.9% Aros

nC16

Ph

(b)

EnhancedMineral Oil
nC14

98.1% Sats
Pr

1.5% Aros

4. Contamination assessment and correction for oil-based drilling uids Oil-based drilling uid systems are particularly benecial in deepwater environments as they do not hydrate active clay minerals and cause them to swell, as can occur in water-based systems. The downside is that most oil-based muds include components with strong physical and chemical similarities to produced oil, complicating the interpretation of geochemical and engineering data. Clean up of oil-based contaminants for source-rock evaluation is straightforward, usually involving washes with organic solvents (e.g., Clementz, 1979; Peters, 1986). There are three basic types of oil bases: diesels, EMOs, and synthetics. Representative whole-oil gas chromatograms of each are compared in Fig. 3. Diesels include various renery molecular-weightrange cuts rened from crude oils for fuel. Their composition varies with the original crude composition and the distillation-cut process. Some so-called dirty diesels show a broad molecular-weight range and bear a strong resemblance to unrened crude oils, including signicant concentrations of biomarkers. EMOs are basically diesels that have been further rened to remove most aromatic hydrocarbons. EMOs typically contain 12% aromatic hydrocarbons with the remainder being saturates. They provide most of the drilling advantages of diesel while meeting oshore regulations for some geographic regions. Synthetics are oil-wet bases that contain double bonds or functional groups promoting environmental breakdown in water. These are usually based on olens, esters, or mixtures of the two compound classes. The olen-bases typically have API gravities in the mid-40 range, while esters are in the lower-30 range. There are some drawbacks to their use in drilling, including greater expense and a loss of functionality at extreme

Ph

Synthetics
(c)

Olefins

Esters

Fig. 3. Examples of whole-oil gas chromatograms of common oil-wet drilling uid bases.

temperatures. Synthetics are currently required for oshore drilling in a number of countries, such as the United States, and their overall use is increasing worldwide. Signicant strides have been made over the last decade to reduce mud-contamination in WFT tools, notably pump-out modules that allow formation uids to be pumped through the tool for clean-up prior to sampling (Colley et al., 1992; Smits et al., 1995). Nonetheless, WFTs typically still show some level of mud contamination (Hashem et al., 1999). Fig. 4 compares a clean DST oil to an EMO-contaminated WFT sample from the same reservoir interval and the EMO-base used in the drilling mud. As DSTs typically involve owing large volumes of oil through the drill stem (100s1000s of barrels), they very rarely show any overprint of oilbased mud contamination and physical properties such as gravity can be measured directly. DSTs in deepwater are very expensive, however, and often only small volume WFT samples are taken to reduce costs. To accurately assess properties of the reservoir oil it is necessary to correct uid properties measured on the contaminated WFT, which requires an estimation of percent contamination. Percent contamination estimates are based on gas chromatographic analyses of the contaminated uid and associated mud ltrate, if available.

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DST Oil
nC12 nC16

(a)

0% EMO
nC25

nC16

WFT Oil
nC12

(b)

9.2% EMO
Ph Pr

nC16
(c)

EMO-Base

Accurate estimation of percent contamination and uid property correction is most dicult for contaminants with many components indigenous to the oil (e.g., diesel, and to a lesser extent EMO). Synthetics are generally easier to correct for, as olens and esters are rarely found in uncontaminated crude oils. The geochemical overprint of EMO-mud can be variable. The base-uid generally represents a narrow molecular-weight-range cut (e.g., C12C21 in Fig. 4), lacks biomarkers, and has a low concentration of aromatics with a distinctive signature. Drilling muds are often re-used between wells, however, and may become contaminated with crude oil or drilling additives from other wells. Therefore, contaminated oil samples (e.g., WFTs) must be compared to mud-ltrate pressings from the same well, rather than the pure base-oil. An example illustrating the geochemical interpretation of highly contaminated samples is shown in Fig. 5. Only sidewall core (SWC) samples were available for identifying a potential oil rim on a gas reservoir. Because the well was drilled with an over-balanced mud

MCH

MCH

Pr Ph

nC25

nC12

1.0

(a)

Oil-Zone SWCs Base Gas Reserv. Oil DST & WFT Tests

Sats / Aros + Sats

Pr Ph

0.9 0.8 0.7 0.6 0.5 0.4 0 20 40 60 80 100

Fig. 4. Comparison of whole oil GCs of uncontaminated DST oil, WFT oil from the same reservoir zone, and the EMO-base used in the drilling mud. The 9.2% EMO contamination in the WFT oil was estimated by GC subtraction (see Section 4 in text).

EMO Mud

Fig. 4(b) shows a WFT contaminated with the same EMO-base shown in Fig. 4(c). The degree of contamination is determined by subtracting the mud ltrate from the contaminated uid signature, or, if no ltrate is available, by subtracting the portion of a contaminated chromatogram in excess of a smooth trendline t for unaltered peaks or for the unresolved complex mixture hump (biodegraded oils). This approach assumes that contaminants are GC-resolvable, an assumption that has been substantiated through analysis of prepared mixtures of clean DST oil with EMO-base, and through addition of and analysis for deuterated tags in the drilling mud. Once the percent contamination is estimated, correcting API gravity, GOR, and uid volumetrics (e.g., shrinkage or formation-volume factor) is fairly straightforward and is routinely performed by PVT service laboratories. These corrections are based on calibrations developed using experimental mixtures of oil and contaminant (e.g., EMO). Contaminated live-oil viscosity and saturation pressure measurements are more dicult to correct as they require equation-of-state modeling (Gozalpour et al., 2002; Bergman, 2003).

% EMO-Based Mud Filtrate Contamination

0.55

3 MP / 1,3 DMP + 3MP

(b)
0.50

No Show Fair Show

0.45 0.40 0.35 0.30 0.6

Good Shows

EMO Mud

Base Gas Reserv.

0.7

0.8

0.9

1.0

1.1

1.2

1.3

3+2 / 9+1 Methyl Phenanthrenes

Fig. 5. Evaluation of a possible oil rim at the base of a gas reservoir using contaminated sidewall cores (SWCs). Gas reservoir was highly invaded with EMO due to overbalanced drilling. Gas reservoir SWCs were compared to SWCs and tests from nearby oil reservoirs. Although EMO has low-aromatics (a), distribution of phenanthrene isomers (b) is distinctive.

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system, the near-well-bore region was heavily ushed by mud and SWCs were all highly invaded with EMO. Solvent-extracts of SWCs from the base of the gas reservoir were analyzed and compared to the EMOmud used, as well as to SWC extracts from nearby reservoirs where oil was tested (DST and WFT oils were also analyzed). A high content of saturates in the gas reservoir extracts conrms extensive EMO contamination due to mud invasion. The DST oil was clean, and the ve WFT oils contained EMO contamination between 2% and 18% (Fig. 5(a)). The severe contamination of the SWCs made it dicult to evaluate the presence of indigenous oil. However, despite the fact that aromatic content of the EMO is low, its distinct distribution of phenanthrene isomers allowed discrimination from indigenous oil (Fig. 6). The quality of the oil show was assessed from specic phenanthrene ratios, assuming that a gas zone, lacking indigenous aromatics, would show only an EMO-dominated phenanthrene signature. On this basis, SWCs through nearby oil reservoirs ranged from good (phenanthrene ratios matched oil tests) to no-show (possibly a non-reservoir zone between oil horizons or completely ushed by mud). SWCs from the base of the gas reservoir showed an EMO-dominated phenanthrene signature, consistent with a lack of indigenous oil (Fig.

5(b)). This evidence, plus the dry, biogenic character of the gas (based on molecular and isotopic compositions) indicated that there was no oil rim at the base of the gas reservoir.

5. Water-based drilling uids: composition and component functions There has been a trend toward the use of higher salinity brines in both water and oil-based mud, because they allow superior activity control for swelling-prone clay minerals. The generalized composition of oshore and onshore water-based muds is shown in Fig. 7. The continuous phase is typically potassium or sodium chloride brine. Calcium chloride brines, used for the discontinuous phase of oil-based muds, are specically avoided as a continuous phase because they adversely impact mud viscosity and uid loss. For onshore drilling operations, diesel often serves as the discontinuous phase of water-based muds because of its improved drilling properties. The potential presence of diesel in such muds is important to consider when evaluating the geochemistry of onshore oils and rocks. Bentonite clays and gels are the predominant viscosiers in water-based muds. Lignosulfonates and lignite coals

DMPs
P
9 1 3 2

DST Oil

EMO Mud System

3+2 > 9+1 Me-Phen C2-Phens < Phen

No EMO Contamination
3+2 << 9+1 Me-Phen C2-Phens > Phen
2 3 9 1

DMPs

C1-P

C2-P C3-P

C1-P

SWC in Oil Zone Excellent Show

SWC in Oil Zone

Fair Show

C2-P C3-P

SWC at Base of Gas Zone

No Oil Rim

m/z m/z m/z m/z 178 192 206 220

C2-P C3-P

C1-P

C1-P

Fig. 6. Aromatic GC/MS scans from Fig. 5 example. Combined ion chromatograms for m/z 178 (phenanthrene), m/z 192 (methyl phenanthrenes), m/z 206 (C2-phenanthrenes), and m/z 220 (C3-phenanthrenes) are displayed. Distributions are very dierent between indigenous oil (uncontaminated DST) and EMO-mud, which allows identication of in situ oil in highly invaded SWCs.

C2-P C3-P

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Water-Based Mud
Weight % (excluding weighting agents):

Pr

Sulfonated Asphalt Additive

offshore
polymers (K,Na)Cl* bentonite

onshore
diesel

Source Rock Extract GC

Ph

nC22

Aqueous Fluid

Aqueous Fluid
Sulfonated asphalt: TOC: ~35 wt. % HI: ~600
Fig. 8. Whole extract GC of source-rock SWC contaminated with sulfonated asphalt additive used in water-based mud as a shale stabilizer. The high TOC and hydrogen index of the additive interfere with source evaluation and must be cleaned up prior to analysis.

*Increasing salt contents with time

Fig. 7. Generalized distribution of components in water-based drilling muds (in wt%, excluding weighting agents).

are added for ltration control. Lignite may impact geochemical interpretation of SWC and cuttings extracts, as it imparts an immature signature to saturate biomarker distributions. Water-based muds are kept alkaline with sodium hydroxide. The calcium hydroxide favored in oil muds is not used because of problems associated with calcium in water-based systems. Finally, a wide variety of polymers are used in water-based muds to address an array of potential drilling problems. In the past, water-based mud systems imparted few contaminants to impact geochemistry and uid properties. Today, water-based mud systems, especially those used in the deepwater with additives to control swelling clays and gas hydrate formation, can signicantly complicate geochemical interpretations. A whole-extract gas chromatogram of a deepwater source-rock penetration from a well drilled with waterbased mud is shown in Fig. 8. The initial straight-hole well was lost due to sticking drill pipe as a result of encountering active, swelling clays. To get the sidetracked well down, a shale-stabilizer additive, based on sulfonated asphalt, was used in the water-based mud. As a result, all SWC and cuttings samples were contaminated. An important objective of this well was to evaluate source characteristics and hydrocarbon potential. However, source evaluation was signicantly compromised by the sulfonated-asphalt additive, which had a total organiccarbon content of approximately 35 wt% and a RockEval hydrogen index of about 600 mgHC/gTOC. The problem was solved by exploiting the polarity of the contaminant for clean up. SWCs were solvent-extracted with dichloromethane (DCM) and then subjected to liquid chromatography. The high polarity of the sulfonated asphalt allowed it to be completely removed from the rock by DCM extraction. Liquid chromatography (LC) allowed for separation of indigenous saturate and

aromatic hydrocarbons from the sulfonated-asphalt additive. The broad, multiple-peaked character of S2-pyrograms from Rock-Eval analyses of contaminated samples were reduced after cleaning, suggesting that TOC and Rock-Eval hydrogen index values determined on the solvent-extracted rocks were valid. Biomarker analyses were conducted on the cleaned saturate and aromatic hydrocarbon LC fractions. As a result, source rock-to-oil correlation and vertical source-rock variability were constrained. Although they did not appear to impact the TOC, Rock-Eval or biomarker signatures, other organic contaminants added to the water-based mud used in this well, including polyglycerols, xanthan biogum, starch, and polyanionic cellulose, could potentially impact other organic geochemical analyses. Water-based mud was also used in a second deepwater well from this area. Drilling problems meant that uid tests (e.g., WFTs) could not be taken. Oil shows were recovered from the mud pit, but were highly contaminated by a water-based additive (Fig. 9). Potential source rocks were penetrated but were also highly contaminated. The nature of the contaminant had to be determined to accurately evaluate uid properties and source potential. The contaminant was determined to be polyalkylated glycol. Glycols are added to water-based muds used in deepwater wells as anti-freeze to prevent the formation of solid gas hydrates through freezing-point depression. In order to correct uid properties measured on glycol-contaminated samples, a calibration for hydrocarbon-glycol mixtures would have to be made. These calibrations were not carried out because of the eort required, and consequently uncertainties still remain about reservoir uid properties.

nC26

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: Polyalkylated glycols

Mud Pit Oil Show Whole Oil GC

Fig. 9. Whole oil GC of oil-stained mud collected from mud pit. Polyaklylated glycols were added to the water-based mud to prevent gas hydrate formation. Glycols interfere with both extract/oil analysis and source rock screening (TOC, RockEval). Glycols can be removed from saturate and aromatic fractions, but are dicult to fully remove from source rock samples.

An attempt was made to clean rock samples for source rock analyses using DCM-extraction followed by liquid chromatography. While liquid chromatography yielded clean saturate and aromatic fractions for biomarker analyses, even multiple DCM extractions of the rock samples could not remove all glycol compounds, probably due to strong bonding with the clays. Rock-Eval data, in particular, still appeared to be highly compromised. Although not attempted in this situation, Barnard et al. (2001) report that satisfactory Rock-Eval data can be obtained when polyalkylated glycol contamination is removed using a polar solvent mix of methanol, acetone and water. When a third deepwater well was drilled in the same area, oil-based (EMO) mud was used. There were no signicant diculties with the drilling of this well and uid property and geochemical interpretations were relatively straightforward. Although geochemists have traditionally complained about the use of oil-based mud and advocated drilling with water-based systems, these examples suggest that times have changed. Oil-based mud systems are actually preferable now to water-based, as they generally have a more predictable and correctable impact on uid properties and geochemistry.

6. Well-test and completion uids: potential sources of calcium contamination Many recent deep-to-ultra-deepwater oil discoveries are biodegraded. This is a function of shallow reservoir depths, low geothermal gradients, and cooling ef-

fects of large water columns (Wenger et al., 2002). Biodegraded oils tend to be relatively acidic, with high TAN (e.g., Robbins, 1998; Olsen, 1998; Meredith et al., 2000) and high CO2 contents in solution gas (Wenger et al., 2002). Due to the hydrophilic nature of the carboxylic acid group, organic acids (especially naphthenic acid) tend to concentrate near the oil-water contact. Naphthenic acids formed during biodegradation can complex with metal cations from formation water to form naphthenate salts that act as natural surfactants (Goldszal et al., 2002a,b). Metal naphthenates may partition into oil- or water-phases depending on the system pH. In the oil-phase, naphthenates deteriorate oil-quality and value as they can cause corrosion and must be removed or stabilized prior to rening. In the water-phase, naphthenates can result in serious scaledeposition problems in separators, de-salters and topside facility tubulars, disrupting production operations. Calcium naphthenate is particularly insidious, as it is mutually soluble in both oil and water under typical reservoir production conditions. Its presence promotes tight emulsions that require additional processing, severely impacting deepwater development economics. During production, changes in separator pH can lead to localized scaling (Rousseau et al., 2001). Depressurization or an increased water-cut during production can lead to additional CO2-release, impacting pH (Dyer et al., 2003) and intensifying scaling problems through the production string. Although naphthenate salts have not received much attention in geochemical literature, they are widely recognized in engineering literature as the cause for severe scale problems in West Africa and Venezuela (Rousseau et al., 2001), the North Sea (Vindstad et al., 2003), and Indonesia (Gallup et al., 2002). Calcium in oil is a rening problem that impacts the use and consequently the value of biodegraded oils. Calcium content of oil is typically monitored at the renery as part of the crude assay analysis. High organic-calcium contents translate to high-ash contents. High-Ca, highash oils can not be cracked to suitable fuel oil for power plants as they can damage power turbines. Low-Ca, lowash oils, even if they are heavily biodegraded, are commonly used for this purpose. Consequently, calcium content is closely monitored and high-Ca oils typically incur heavy debits. Although organically bound, oil-associated calcium is the primary cause of rening problems that lead to decreased oil value. However, some of the measured calcium in DST oils may represent calcium contamination from completion brines emulsied with the oil-phase. The example summarized in Fig. 10 shows high calcium contents measured by renery assays for a set of DST oils. If the high calcium contents were real, representing primary petroleum compositions, signicant oil-value debits

nC10

nC14
Pr Ph nC 19

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(a)

All Samples by Test Type & Processing

EMO DST (Centrifuged) DST (Assay)
1600

(b) Individual Reservoir by

Test Type/Processing

Calcium (ppm)

Ca (ppm)
754 48 3 3

1200 800 400 0

WFTs (Centrifuged)

Severely Biodegraded Oil (no DST)

Fig. 10. Calcium content as a function of test type and processing. Several DST oils had high original calcium contents. By centrifuging prior to analysis, calcium content was signicantly reduced. Analyses of separated water phase indicated contamination by CaCl2 completion uid used in the DST procedure (a). WFT samples are relatively uncontaminated. Comparison of samples from the same reservoir by test type and processing protocol (b) show the magnitude of contamination in DST samples. High calcium contents in two severely biodegraded WFTs appear to represent real organic calcium.

and additional processing and facilities costs would be incurred. If they could be identied as contamination (from DST completion uids), large oil-value debits and additional processing facilities would be avoided, signicantly improving development economics. Both DST and WFT samples, many of which came from the same reservoir in the same well, were analyzed to assess potential calcium contamination. Samples were centrifuged rst in an attempt to separate any emulsied water from the biodegraded oil, a step not traditionally taken prior to renery assay. Both oil and water phases were analyzed. Chloride content of the oil samples was measured by X-ray uorescence (XRF) to assess amount of emulsied water remaining. Calcium and other cations were measured on both oil and water phases by inductively coupled plasma-atomic emission mass spectroscopy (ICP-AES). Results indicate the bulk of calcium in the DST oils could be separated by centrifuging (Fig. 10(b)). WFT samples from equivalent zones had very low calcium contents. Analyses of the water phase separated from DST oils indicated a composition representing pure calcium chloride brine (as used in completion uids), not natural formation water. These results showed that most of the calcium in the original DST oils were related to contamination from completion uids (300,000 ppm calcium-chloride brine used as a cushion in the well-bore prior to the initiation of the DST ow). Only two WFT oils from the same well, both severely biodegraded, appeared to contain signicant levels of organic calcium (Fig. 10(a), no DST was taken in this well). These oil reservoirs were not under consideration for development, due to the presence of oil with very low API gravity, high viscosity and high TAN. As a follow-

up, all DST oils collected from this region are now routinely subjected to a multi-stage water-washing/centrifuge step followed by ICP and XRF-analyses. Primary (real) organic calcium is that remaining after essentially all chloride has been removed. Although DST oils showed the bulk of the calcium contamination due to their interaction with pure (300,000 ppm) CaCl2 completion brines, WFT oils could also have minor levels of calcium contamination. Although never in contact with completion uids, WFTs from this area are contaminated with 220% of the EMO drilling mud used (estimated by method described in Section 4). The EMO-based mud includes calcium from discontinuous phase CaCl2 brines, Ca(OH)2 added for alkalinity and a small amount from fatty acid soaps (see Fig. 2). The water phase of the EMO-mud only represents 25% of the total uid, and EMO contamination in the WFT oils is less than 20%, so calcium contamination in WFTs is probably not signicant. This is supported by the fact that calcium contents in the WFT samples were not signicantly reduced by centrifugation prior to analysis. 7. Summary Observations and conclusions of this work are as follows: 1. Modern deepwater drilling and completion uids can signicantly impact geochemical and uid property data. 2. Accurate evaluation of contaminated uids and rocks should involve analysis of the drilling uid, from the mud ltrate if possible, and the contaminated sample. Sometimes this requires analysis of both oil- and water-phases.

un-centrif. centrifuged

DST DST WFT WFT Assay centf. centf.

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L.M. Wenger et al. / Organic Geochemistry 35 (2004) 15271536 International Symposium on Oileld Scale, Aberdeen, United Kingdom, 2930 January, p. 14. Gallup, D.L., Smith, P.C., Chipponeri, J., Abuyazid, A., Mulyono, D., Kelland, S.-J., Jones, D.M., 2002. Formation and mitigation of metallic soap sludge, Attaka, Indonesia Field. In: SPE 73960, Society Petroleum Engineers International Conference on HSE in Oil and Gas Exploration and Production, Kuala Lumpur, Malaysia, 2022 March, p. 16. Goldszal, A., Bourrel, M., Hurtevent, C., Volle, J.-L., 2002a. Stability of water in acidic crude oil emulsions. In: AIChE 4th International Symposium on the Chemistry and Physics of PetroleumWater Emulsion II, Paper No. 56f. Goldszal, A., Hurtevent, C., Rousseau, G., 2002b. Scale and naphthenate inhibition in deep-oshore elds. In: SPE 74661, Society Petroleum Engineers Oileld Scale Symposium, Aberdeen, United Kingdom, 3031 January, p. 11. Gozalpour, F., Danesh, A., Tehrani, D.-H., Todd, A.C., Tohidi, B., 2002. Predicting reservoir uid phase and volumetric behavior from samples contaminated with oilbased mud. SPE Reservoir Evaluation & Engineering 5 (3), 197205. Hashem, M.N., Thomas, E.C., McNeil, R.I., Mullins, O., 1999. Determination of producible hydrocarbon type and oil quality in wells drilled with synthetic oil-based muds. SPE Reservoir Evaluation & Engineering 2 (2), 125133. Meredith, W., Kelland, S.-J., Jones, D.M., 2000. Inuence of biodegradation on crude oil acidity and carboxylic acid composition. Organic Geochemistry 31, 10591073. Olsen, S.D., 1998. The relationship between biodegradation, total acid number (TAN) and metals in oils. American Chemical Society Petroleum Chemistry Division 43 (1), 142145. Peters, K., 1986. Guidelines for evaluating petroleum source rock using programmed pyrolysis. American Association of Petroleum Geologists Bulletin 70 (3), 318329. Robbins, W.K., 1998. Challenges in the characterization of naphthenic acids in petroleum. American Chemical Society Petroleum Chemistry Division Pre-print 43 (1), 137140. Rousseau, G., Zhou, H., Hurtevent, C., 2001. Calcium carbonate and naphthenate mixed scale in deep-oshore elds. In: SPE 68307 presented at 2001 Society Petroleum Engineers 3rd International Symposium on Oileld Scale, Aberdeen, United Kingdom, 3031 January, p. 8. Smits, A.R., Fincher, D.V., Nishida, K., Mullins, O.C., Schroeder, R.J., Yamate, T., 1995. In situ optical uid analysis as an aid to wireline formation sampling. SPE Formation Evaluation 10 (2), 9198. Vindstad, J.E., Bye, A.S., Grande, K.V., Hustad, B.M., Hustvedt, E., Nergard, B., 2003. Fighting naphthenate deposition at the Heidrun Field. In: SPE 80375 Presented at 2003 Society Petroleum Engineers 5th International Symposium on Oileld Scale, Aberdeen, UK, 2930 January, p. 7. Wenger, L.M., Davis, C.L., Isaksen, G.H., 2002. Multiple controls on petroleum biodegradation and impact on oil quality. SPE Reservoir Evaluation & Engineering 5 (5), 375383. World Oil, 2003. World Oils Fluids 2003: Classications of Fluid Systems. World Oil, June 2003, pp. F1F34.

3. In some cases, contaminated samples can be cleaned up, or data can be mathematically corrected. 4. Biodegraded oils in deepwater reservoirs are associated with a number of components (e.g., acids and naphthenates) that bring new challenges to development and production engineering (emulsions, scale) and rening (corrosion, ash). An understanding of the chemistry, physical properties and interaction of indigenous and operation-added materials is critical to mitigating the economic impact of such oils.

Acknowledgements The authors thank the management of ExxonMobil Upstream Research Company for permission to publish this work. ExxonMobil colleagues Marty V. Smith (drilling uids), Gordon L. Kornfeld (uid testing), Winston K. Robbins (naphthenic acids and naphthenates), and W. Lee Esch (water chemistry) are gratefully acknowledged for subject matter input and productive discussions. Core Laboratories Pencor Division is acknowledged for assistance in method development for wireline oil test percent contamination corrections. GeoChem Laboratories, Inc. assisted in development of the sulfonated asphalt removal procedure. Critical reviews of the manuscript by Ted Bence, Marc D. Norman, Brad J. Huizinga, two anonymous reviewers, and editorial handling by Guest Associate Editor Erdem Idiz improved the manuscript, are appreciated. Guest Associate EditorErdem Idiz

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