saneno19 “The Leading Edge - June 2016 -Etfect of Chemical Diagenesis on Pore Pressure in Argiaceous Sediment Effect of Chemical Diagenesis on Pore Pressure in Argillaceous Sediment Nader C. Dutta ? Abstract | present a model of pore pressure for argillaceous sediment that integrates the well- known undercompaction mechanism with the lesser-known chemical diagenesis mechanism. The model is based on a generalized compaction model, first-order chemical rate theory and Arrhenius rate equation, and a simple thermalhistory model. The parameters of this model (activation energy, E, and the pre-exponential factor, A) are obtained from published X-ray diffraction data. | also present models for bulk density and velocity of sediment that are guided by rock-physics principles. | also discuss the relation between the current model and the Bowers model, which noted the importance of the thermal mechanisms in the context of pore-pressure prediction. Introduction Accurate predrill prediction of pore pressure is very important for exploration, drilling, and resource estimation. The Eaton method (Eaton, 1975) has been used widely for pore-pressure prediction. In this method, one first constructs a so-called normal compaction trend (NCT) of an attribute (e.g., velocity) and then uses a deviation from this trend as a measure of high pore pressure through a parameter known as the Eaton-exponent (typically 3 for velocity). The Eaton method assumes that the higher pore pressure is caused only by undercompaction of sediments. In his noteworthy publication, Bowers (1995) suggested that inclusion of thermal mechanisms is essential to account for very high pore pressure in many clastic basins hitpshwwleonine.orgitheleasingedge/june_2016/MoblePagedArtile.acon?artelld=97127SKartclels@71275 a3torrente “The Leading Edge June 2016 - fet of ChomelDiageness on Pore Pressure h Arglaceous Sediment and that mechanical compaction alone could underestimate pore pressure by as much as 4 pounds per gallon (ppg). Bowers further suggested that to account for thermal effects in an empirical way, the Eaton-exponent should be variable — say, 5 instead of the traditional value of 3— and, perhaps, there should be an NCT shift. He termed the various thermal mechanisms as "fluid expansion.” Dutta (1986, 1987) proposed an earlier version of an integrated model in which both undercompaction and chemical diagenesis models were combined using a chemical kinetic theory and suggested a way to predict pore pressure using a simple thermal- history model. The parameters of the model were estimated for the specific case of smectite-to-ilite transition (S/1) using the X-ray diffraction data of Hower et al. (1976). Smectite is a type of clay mineral (e.g., montmorillonite) that undergoes reversible expansion upon absorbing water, whereas illite is a clay mineral of the muscovite mica group with a lattice structure that does not expand upon water absorption. Here, we outline the model's essential steps and propose a relation (crossplot) between the velocity and the density of shales undergoing S/I transition. This model is predictive; a simple thermal-history-based model through the use of a parameter called diagenesis function (defined as B in the development presented here) dictates the onset of chemical digenesis and the alteration of the acoustic properties of shales (density and velocity) In this paper, | present an explicit relation between velocity, density, and the fundamental geologic variables such as effective pressure, porosity, temperature, and geologic time. The model enables us not only to predict a smooth transition between the mechanical and chemical diagenesis from a knowledge of the thermal history of shales, but also to provide a guide for estimating the depth at which diagenesis begins, the shape and extent of the transition zone, its effect on the pore-pressure buildup, and the relation between density and velocity of rocks. A generalized compaction model Dutta (1986) proposed a generalized compaction model that included temperature, T, in the shale compaction, and proposed the following relation between the vertical effective stress, 0, and void ration, €: hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 23saneno19 “The Leading Edge June 2016 - Effect of Chemical Diagenesis on Pore Pressure in Argliaceous Sediment o= 06%? EB IT) 8. @ Here the void ratio, ¢, is defined as the ratio of the pore volume of a rock to that of the solid rock, namely, e=9/ (1-9). Q) In equation 1, 00 is a normalization constant and B(T) is termed as the diagenesis function that depends on T. We will see below that T is a function of geologic time, t. Its explicit form was given by Dutta (1986), and a slightly modified form was given in later publications (Dutta et al., 2014). The generalized compaction model, as introduced here, suggests that vertical effective stress can change without changing porosity — a feature common to chemical diagenesis; it is not possible if undercompaction is the only mechanism. From Terzaghi's law, gis related to pore pressure, P, and vertical overburden stress, S, by o=S-iP. ) Here, A is the Biot’s consolidation coefficient and is taken to be unity. A model for diagenesis function, B (T) Chemical diagenesis includes any chemical process that changes the properties of the host rock matrix by chemical reactions, such as smectite-illte (S/l), kaolinite-chlorite, and illitemuscovite in shales, and gypsum-anhydrite in carbonates diagenesis, and various kerogen-conversion mechanisms in organic-rich rocks (such as Kimmeridge shales in North Sea and Bakken Shales in Williston Basin in North America, and organicmaterial-rich carbonates in the Middle East). In the example given below, | specifically address the S/I chemical reaction, which is the most studied reaction as given below: Smectite K-feldspar mica = illite chlorite HzO quartz hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 ans.torrente “he Leading Edge June 2016 - fet of ChomclDiageness on Pore Pressure h Arglaceous Sediment K-feldspar is the catalytic converter in the reaction. Hower et al. (1976) concluded that the S/I diagenesis: (a) contributed to increasing fluid pressure within the shales; (b) affected the adjacent reservoir rock quality by decreasing its permeability due to migration and subsequent precipitation of finely divided silica produced during S/I transformation; (c) caused a long-range ordering of smectite and illite layers, thus causing increased anisotropy due to layering; and (d) collapsed the clay platelets in the host shales, thus changing the vertical effective stress. In the following discussions, | model the S/l transformation. The model assumes that the S/I reaction can be expressed by a first-order chemical rate theory, namely: AN, ( /dt=- KN, (0, 4 where Ne(t) is the molar fraction of smectite in the host rock at time, t, and K is the rate constant. The Arrhenius equation gives this relationship between K and the temperature, T (in °k), as follows: K-Act®, 6) where A is the frequency or the pre-exponential factor, E is the activation energy, and R is the universal gas constant. At higher temperatures, the probability of molecular collision increases, leading to a higher kinetic energy, which affects the activation energy of the reaction. The activation energy is the amount of energy required to ensure an occurrence of the reaction. The pre-exponential constant, A, is the number of collisions (leading to a reaction or not) per second occurring with the proper orientation to react, and e©/RT is the probability that any given collision will result in a reaction. It can be seen that either increasing the temperature or decreasing the activation energy (for example, through the use of catalysts, as in the S/I reaction) will increase the rate of reaction. Combining equations 4 and 5 and integrating with respect to t, the smectite fraction, Nz (t), remaining at time, t, is given by NW) =N(O) Exp LE dept |E hd. 6 } where N,(0) is the starting molar fraction of smectite at t = 0. The diagenesis function, B, in equation 1 is related to equation 6 as follows: hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 angsaneno19 “The Leading Edge - June 2016 - Effect of Chemical Diagenesis on Pore Pressure in Argliaceous Sediment B=B,N.t) +B, O-N,@), (a) where Bo and By are constants. If we assume that the present-day geothermal gradient, a, did not change during the paleo time, and To is the reference temperature — say, the sea-bed temperature — then the temperature, T, at a given depth, Z(t), is: T@=T,+aZi0, (3) ZO=rt (8b, and, thus, the temperature-time relation becomes TO=T+ayt (8c) Here, vis the constant burial rate between time t = 0 and t. In actual numerical applications, | approximated the burial rates by piecewise linear functions in smaller time steps (layers) with varying burial rates within each layer. Equation 8c depends on the product (ay), and it is termed as the rate of heating. Therefore, the extent of diagenesis is controlled by the time duration of the material (smectite) staying in a given time-temperature window and not by temperature alone For the activation energy and the frequency factor of equation 5, Dutta (1987) obtained E = 19.3 + 0.7 Keal / mole and A = 0.105 x 4 (yr.)"" by using the data from Hower et al (1976) and others. These values were further confirmed by using more data from basins outside the Gulf of Mexico (Dutta et al., 2014). Figure 1a shows a plot of the diagenesis function, 8, for a sedimentary basin that has undergone the typical subsidence of the Miocene age with a constant thermal gradient of 1.2°F/100 ft. The first derivative of the curve in Figure 1a is related to the amount of bound water released as the result of diagenesis (see Figure 1b). The temperature, Tm, at which the peak water release occurs, i.e., dNs(t)/dt = 0 in Figure (1b), is given by the transcendental equation: E/(RT,) =In (ART? )/(yaE). eo) Figure 2a shows the variations of the illite fraction, (1-N, (t)), of equation 6 for the indicated constant burial rates at a fixed thermal gradient of 1.2°F/100 ft. Figure 2b hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 si3se2018 “The Leacng Edge - une 2016 -Etfect of Chemical Diagenesson Pore Presse in Argiaceous Sediment shows the variation with respect to different thermal gradients for a fixed burial rate of 1fl/1000 years. These figures clearly show the kinetic nature of the current model — older rocks and rocks with higher temperatures begin the S/l transition at shallower depths, while the opposite is true for younger rocks and lower temperatures. The midpoint transitions differ by ~10 kf T \undercompaction \ Dept) Depth (a) chemical diagenesis regime Dingenesis function, Thermal gradient =0.012°F'N. ‘Bur ate = 1.0 kfUilion years Bul Hite Fxcton Mite ection The generalized compaction model given in equation 1 indicates that as the effective stress in the sediment increases, the porosity decreases for a fixed B value. This is the so-called undercompaction process. However, the model also shows another process in which the porosity change is negligible but the effective stress changes significantly due to shale mineralogic changes. This is the diagenesis process of Dutta (1986), and it is similar to the fluid expansion process of Bowers (1995). However, in the model hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 enstorrente “he Leading Edge June 2016 - fet of ChomclDiagenesson Pore Pressure h rglaceous Sediment presented here, the transition from undercompaction to chemical diagenesis is a gradual process dictated by the time-temperature history of the sediments and not depth as a single variable. Effect of diagenesis on velocity and density of shales Dutta et al. (2014) proposed the following relation between slowness (A1), effective stress, a, and the diagenesis function, : Ar = Ar, (1+ #8 In (a,/0)). (10) Here, m denotes the rock matrix x and is a lithology-dependent exponent. The above relation is valid for porosities less than the critical porosity, ,. Above «, the sediments are suspensions (solid and water), and the velocity is governed by Wood's model. Below ¢, the sediments are load bearing. The S/ transformation significantly affects the bulk density, p, of shales as shown by Dutta (2002). A slightly refined version of the pre-and postdiagenetic trends (labelled as Eo- and Telo-genesis in Figure 2 of Dutta, 2002) are shown in Figure 3. The end- member trends (solid lines) are based on analyses of wells from several parts of the world. The data in Figure 3 are from a specific well. The rocks are of Miocene- Oligocene age. The color codes indicate depths. The pink curve is the predicted evolutionary path from the model for this particular well. The model and the data are in agreement. There were no CEC or X-ray diffraction data available for this well — just the logs. This figure clearly shows that the smectitic shales have a trend distinctively different from that of the ilitic shales. Thus, one can predict the density-velocity relationship of every point on the crossplot by knowing the thermal history. The diagenetic trend of Figure 3 is of the following form: hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 m3saneno19 “The Leading Edge June 2018 - Effect of Chemical Diagenesis on Pore Pressure in Argliaceous Sediment Depth (ft) 29 io Dats select for shale only he / 28 2i ue pes g 14 Bas 2 12 2 24 aa, " 2.2) New densi model jos nee an \ jos 4030100120140 160 t80 I Slowness (hs/ft) p=p(N() +p,0-NO), an a2) (13) Here, p, and p; are the end-member smectitic and illitic shale trends, respectively. Ar is the interval transit time or slowness, and a, b, c, and d denote calibration constants. Katahara (2006) also observed a similar trend and validated these trends. Diagenesis also alters the matrix properties of shales characterized by Atm, and x. To account for this effect in equation 10, the terms containing Atm and * are modified by using the diagenetic function, N, (t), of equation 8 as follows: = At,,,N() + Ar, (1- NiO), (4) =x.N.{t) +x(1-N.Q), as) where Atm,s and Am, denote, respectively, the slowness for smectite and illite grains. We note that equation 10 will yield the slowness for normal compaction, Arp, if the effective stress is computed using normal pore pressure. The NCT-trend thus derived is supported by the rockphysics considerations; it is not curvefitted to a particular well data and can be used to carry out the traditional Eaton approach for pore-pressure prediction, if desired, as given below: a=o, (At, / At)", (14) hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 ans.se2018 “The Leacng Edge - une 2016 -Efect of Chemical Diagenesson Pore Presse in ArgiaceousSeximent where Gr is the effective stress under normal pressure condition. This approach will remove the guesswork in constructing an NCT in the Eaton method, since it is predicted by the diagenesis function appropriate for the burial conditions of the sediment under hypothetically assumed normal-pressure condition. This approach may also eliminate the need for arbitrary NCT trend shifts often used in the Eaton approach. Figure 4a shows a plot of predicted velocity versus depth corresponding to the diagenesis function shown in Figure 4b that is appropriate for the average Miocene-age shales in the Gulf of Mexico. The thermal gradient is 1.2°F/100 ft. Each curve in Figure 4a corresponds to the indicated pore-pressure gradient in ppg. The rightmost curve in Figure 4a is valid for the normal pressure condition, and it is the predicted NCT from the model. Imprints of diagenesis are clearly seen in these curves — these are not straightline curves in semilog space as required in the Eaton model. Discussions In Figure 5, | carry out a comparison of the Bowers (1995) model on the left with the current model on the right (labeled as Dutta model). Two features are noteworthy in the Bowers model: existence of a single "virgin" compaction curve and a host of "unloading" curves as defined by Bowers (1995) when reversal of effective stress takes place. Further, each unloading curve terminates on the virgin curve. Thus he does not allow for any mineralogic changes during the fluid-expansion phase. Katahara (2006) also noted this. In the Dutta model, mineralogical composition is handled by a host of timetemperature curves in the velocity-effective stress domain. It is difficult to predict at what depth an onset of the transition (from undercompaction to fluid-expansion phase) will occur in the Bowers model without having access to specific well data, especially a density log. In the current model, onset of chemical diagenesis is determined from the thermal history (age and temperature versus depth of shales in a given basin) However, both models reach the same conclusion: thermal effects are important causes of overpressure. hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 anse2018 “The Leacing Edge - June 2016 -Etfect of Chemical Dageness on Pore Presse in ArgiaceousSeximent [a] Reckvelcity verses porepresire [5] Dingenetic fanstion = =. cn i Fa a ° 4 Paha, Sy I 2 i ‘Velocity (m/s) ec al a (b] Duua moe = Yeociy > 9 Tero loccng (stress reversal erg tan. ‘ang BURR vs o008=A Sang Ue eumeiedwe|, —> 2 Ettectve Stose Psi) g sen [oor] vs oare =n. g vo 1 ao ak ficro-sec) hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 1013saneno19 “The Leading Edge June 2016 - Effect of Chemical Diagenesis on Pore Pressure in Argliaceous Sediment tia tetve Ste (ps) In Figure 6, a comparison of the present model to a data set from the Gulf of Mexico as published by Gutierrez et al. (2006) is shown. The well locations are indicated in the map at the upper part of the figure. The solid curves are plots of velocity and effective stress from the current model (equation 10) for discrete sets of diagenesis function (8) as indicated. It does suggest a trend: the data for higher fluid pressure gradients (> 0.8 psi/ft) indicate that undercompaction alone will not explain the occurrence of high pore pressure in these wells. Conclusions Here | presented a quantitative diagenesis model for pore-pressure prediction that integrated two well-known mechanisms for pore pressure in argillaceous sediment in a single model: undercompaction and chemical diagenesis due to S/I transformation. The latter is modeled using a first-order rate theory and Arrhenius model. It is shown that if we have a notion of the time-temperature history of sediments, we can predict both the depth of the onset of chemical diagenesis and its imprint on the magnitude and shape of the pore pressure, velocity, and density versus depth curves. A crossplot of density and velocity clearly shows the onset of S/I diagenesis. hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 11113se2018 “The Leacng Edge - une 2016 -Efect of Chemical Diagenesson Pore Presse in ArgiaceousSeximent The model described here could be further enhanced by a more detailed approach for paleotemperature reconstruction, such as in the traditional basin-modeling algorithms. The author partly accomplished this earlier by solving a time-dependent heat-flow equation (see for example, equation 14 of Dutta, 1987). Acknowledgments Mike Batzle was a great friend and a great colleague of mine. | was the research manager at ARCO Oil and Gas from 1986 fo 1989, and Mike was on my team as the project leader of rock physics. This article was heavily influenced by Mike. His curiosity and asking "why" and "why not" kept me up many nights! Thanks, Mike. I will miss you. I thank Yangjun (Kevin) Liu of Schlumberger for many helpful discussions. Corresponding author: Duttanc@outlook.com Attp://dx.doi.org/10.1190/tle35060523.1. References Bowers, G. L., 1995, Pore pressure estimation from velocity data: Accounting for overpressure mechanisms besides under-compaction: SPE, paper SPE-27488-PA, http://dx.doi.org/10.2118/27488-PA. Dutta, N. C., 1986, Shale compaction, burial diagenesis and geopressures: A dynamic model, solution and some results, in J. Burrus, ed., Thermal modeling in sedimentary basins: Editions Technip, 149- 172. Dutta, N. C., 1987, Fluid flow in low permeable porous media; in B. Doligez, Ed., Migration of hydrocarbons in sedimentary basins: Editions Technip, 567— 595. Dutta, N, C., 2002, Deepwater geohazard prediction using prestack inversion of large offset P-wave data and rock model: The Leading Edge, 21, no. 2, 193- 198, hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 23saneno19 “The Leading Edge - June 2016 ~ Effect of Chemical Diagenesis on Pore Pressure in Argliaceous Sediment http://dx.doi.org/10.1190/1.1452612. Dutta, N. C., S. Yang, J. Dai, S. Chandrasekhar, F. Dotiwala, and C. V. Rao, 2014, Earth model building using rock physics and geology for depth imaging: The Leading Edge, 33, no. 10, 1136- 1152, http://dx.doi.org/10.1190/tle33101136.1. Eaton, B.A., 1975, The equation for geopressure prediction from well logs, SPE, paper SPE-5544-MS, http://dx.doi.org/10.2118/5544-MS. Gutierrez, M. A., N. R. Braunsdor, and B. A. Couzens, 2006, Calibration and ranking of pore-pressure prediction models: The Leading Edge, 25, no. 12, 1516— 1523, http://dx.doi.org/10.1190/1.2405337. Hower, J., E. V. Eslinger, M. E. Hower, and E. A. Perry, 1976, Mechanism of burial metamorphism of argillaceous sediment. 1. Mineralogical and chemical evidence: Geological Society of America Bulletin, 87, no. 5, 725~ 737, http://dx.doi.org/10.1130/0016-7606(1976)87<725%3AMOBMOA>2.0.CO%3B2. Katahara, K., 2006, Overpressure and shale properties: Stress unloading or smectite- illite transformation?: 76th Annual International Meeting, SEG, Expanded A1520- 1524, http://dx.doi.org/10.1190/1.2369809. ‘Consulting geophysicist. hitps:wwvleonine.orgitheleacingedgesjune_2016/MobilePagedArticle.acton?artcleld=97127SHartclela97127 1313