Does complex geochemistry of an oil mean a multi-stage filling history?

In the last few years Zhiyong and I have talked a lot about “top down” petroleum systems, analysis (e.g. He and Murray, 2019), one aspect of which is “geochemical inversion”.  Petroleum is a natural material containing 100’s of thousands of individual compounds, mostly hydrocarbons.  Although the composition is complex it is not random: it encodes signals inherited from the original organic matter as well some related to thermal or biological processes during or after formation.  Geochemists interpret this to provide information on the origin and history of a reservoir fluid.

However, I get nervous when the results of geochemical inversion suggest complicated charge histories which are not matched by an equally complicated geological/tectonic history. Recently I reviewed a paper which suggested eight discrete charge events had contributed to the fill for a cluster of fields. The corresponding burial history looked fairly simple so it was hard to imagine how charge could be anything but smooth and continuous in the area. I have a feeling that interpretations like this arise from a lack of recognition of how heterogeneous fluid compositions can be, even in well-connected reservoirs, charged slowly and continuously by a single source rock.

 

In an AAPG talk last year (Murray and He, 2020) we noted that it is quite common for the oil underlying a gas cap to be undersaturated with gas. This shouldn’t be surprising, given that the rate of filling – which is limited by the rate of kerogen maturation during burial - is of the same order of magnitude as the rate of diffusion driven mixing.  If the kerogen organofacies is not uniform (normal for fluvio-deltaic and fluvio-lacustrine source rocks in particular), and fluids are not fully mixed, we would not expect the fluids in the reservoir to be uniform either. Furthermore, since fluids are expelled over a source rock maturity range from ~ 0.7 to 1.3% Ro (vitrinite reflectance), we would not expect to find a uniform “maturity” signal in most oils either, whether it is based on methylphenanthrene isomer ratios or gasoline range ratios or whatever.

 

My experience of reservoir geochemistry studies, where samples from multiple depths, units and wells within a single field are examined, mostly confirms these expectations: A lot of fields I have looked at do not contain well-mixed fluids, independently of any physical compartmentalisation that may exist. This is hardly a new observation: England (1990) commented on it in relation to the Forties field for example. Indeed, it is more surprising when reservoir fluids are found to be well mixed.  I have seen examples of this too though and it seems to be when (a) geometric factors in migration homogenise fluids before or during their arrival at the trap or (b) thermal disequilibrium accelerates density overturn via convection and therefore mixing. My colleagues and I described the latter process in respect of the remarkably well mixed fluids in the Sunrise gas-condensate field (James et al., 2010). Well-mixed fluids are also quite common in fractured carbonate reservoirs where mixing pathways are short due to polygonal fracturing.  My point in mentioning the unmixed fluids is that geochemical inversion studies frequently base their conclusions only one sample from each particular field or reservoir, without taking this into account.

 

A specific example of geochemical inversion is the interpretation of patterns of biodegradation in terms of reservoir temperature vs. charge history.  Biodegradation, which occurs at temperatures lower than about 80 °C, has easily recognisable effects on oil. The most characteristic feature is the complete or partial loss of the n-alkanes (also called n-paraffins). These straight-chain compounds are easily assimilated by bacteria and gas-chromatograms of biodegraded oils show their depletion relative to the “unresolved complex mixture (UCM)” hump.  Note that no new material is formed here – bacteria do not convert straight chain hydrocarbons into the branched and cyclic hydrocarbons comprising the UCM – the latter are just more resistant to attack. A chromatogram of a crude oil with complete loss of n-alkanes is shown in figure 1.

Fig. 1   Gas chromatogram of a severely biodegraded oil from the Vincent Field, Australia (Murray et al., 2013)

A so-called “polyphase” or “hybrid” oil is one in which it is suggested that more than one discrete charge/biodegradation event occurred. This is usually based on the simultaneous presence of very easily degraded and very resistant compound. An example is the co-occurrence in an oil of n-alkanes and the 25-norhopanes, a group of pentacyclic terpane biomarkers associated with a severe level of biodegradation (Peters et al. 2005 and references cited therein). The n-alkanes are attributed to a component of the charge arriving after the reservoir temperature exceeded 80 °C when biodegradation stopped.  A similar conclusion is sometimes drawn when the gas chromatogram shows prominent n-alkanes on top of a large UCM, as shown here in figure 2.

Fig. 2   Gas chromatogram of a “polyphase” biodegraded oil from the Lady Nora Field, Australia. MCH is methyl cyclohexane, a cyclic alkane which is relatively resistant to degradation

Back in 2005 I worked on a heavily biodegraded oil field in the Middle East.  Being onshore and shallow it had been pattern drilled and there were a lot of samples to play with. Gas chromatograms showed the usual UCM with n-alkanes and resolved peaks from other simple compounds present to variable degree. There was a good correlation between API gravity and the area of GC-resolved peaks relative to the UCM, as shown in figure 3.

Fig. 3   Correlation between the total area of resolved peaks (relative to the UCM) and API gravity of oils from a large oil field in the Middle East region

This correlation was useful in estimating the API and the viscosity (by another correlation) of fluids for which there was insufficient sample for direct measurements.  However, in order to predict bulk properties away from well control, we needed to understand the factors controlling the extent of degradation.  Because there were spatially coherent differences in the degree to which light vs. heavy “fresh” charge overprinted the UCM, I concluded, at the time, that there were multiple stages of charge and degradation. The problem was that the burial history was simple and charge should have concluded more than 100 Ma before present.  At the time, I thought there must have been things in the charge history – perhaps to do with “motelling” or some other migration-related process  - that were not captured in the charge model. However, I revisited the report recently and realised there is another possibility. It goes like this…

 

Several studies have shown that heating of the asphaltene fraction of a heavily biodegraded oil can release fresh oil, complete with the original complement of n-alkanes (Snowdon et al. 2016 and references therein).  Asphaltenes are macromolecules with a composition and molecular structure similar to that of the kerogen from which they were derived (Snowdon et al. , 2016). Laboratory pyrolysis of asphaltenes is thus akin to the artificial maturation of kerogens. Figure 4 shows gas chromatograms (and density, viscosity) of a heavily biodegraded oil from a field in the Middle East region, before and after heating at 300 °C for 12 days and at 350 °C for 10 days.  The thermal stress from these two heating regimes is equivalent to a vitrinite reflectance of 0.8 and 1.3% respectively. 

Fig. 4   Gas chromatograms for the original oil from a large oil field in the Middle East region and after heating as shown. I.S. is the “internal standard” added to assist quantitative analysis

If we can do this in the laboratory, why would it not also happen in nature as a reservoir containing biodegraded oils is buried deeper?  Let’s consider such a reservoir which is continuously buried so that the temperature increases from 80 °C to ~ 120 °C over a period of about 20 Ma. Using the kinetics of asphaltene conversion from laboratory studies, we can estimate that about half of the mass of asphaltenes would be converted to “fresh” oil.  The chromatogram, perhaps like that in Fig. 4B, would show a “polyphase” character, without the requirement of any new charge arriving from the source rock after biodegradation ceased. 

 

What if the reservoir is not heated as high as 120 °C? Could we still get an apparently polyphase oil? I believe so: Some studies (see Snowdon et al., 2016 and references cited therein) have shown that the source of fresh oil in asphaltene heating studies is not only pyrolysis (i.e. the breaking of high-energy covalent bonds). Rather, the cage-like molecular structure of asphaltenes appears capable of encapsulating some of the original oil and preventing it from being biodegraded in the first place. This oil can be released by thermal disruption of the asphaltene clusters at temperatures lower than those required for pyrolysis. Figure 5 shows before and after heating chromatograms for a crude oil which had been severely biodegraded at the surface (following an oil spill). The conditions used, 320 °C for 2 days, create a level of thermal stress similar to that applied to the oil in figure 4B. However, in this case the post-heating oil has lots of n-alkanes and only a very small UCM. I wonder how much of the fresh oil here has been released prior to pyrolysis temperatures being reached.

Fig. 5   Gas chromatograms for the original, biodegraded oil collected after a spill at sea and after heating at 320 °C for two days (from Oudot and Chaillan, 2009)

In almost all cases where complex charge histories are invoked to explain geochemical anomalies, I can (at least in principle) explain them by things that happen during, normal continuous burial and supply of hydrocarbons. This doesn’t mean that the simple explanation is necessarily true - just that, in the absence of evidence for a complex burial/thermal history, we need not be as puzzled as I was back in 2005.

 

As with all these blog posts, I invite and indeed welcome push back/comments/clarification. They are not peer-reviewed papers, just some observations and thoughts from one individual.

Cheers,

Andrew Murray,

References:

England W. (1990) The organic geochemistry of petroleum reservoirs. Org. Geochem., 16, 415-425

He Z. and Murray A. (2019) Top Down Petroleum System Analysis: Exploiting Geospatial Patterns of Petroleum Phase and Properties. AAPG Search and Discovery, #42421

James B., Bailey W, Murray A., Pelechaty S., Kaiko A. and J. Li (2010) Unusual reservoir connectivity revealed by data integration at the Sunrise Field.  APPEA J. 50th Anniversary issue, 349-370, Australian petroleum production and exploration association (A PDF is available from the author on request)

Murray A. and He. Z. (2020) Oil vs. Gas: What are the Limits to Prospect-Level Hydrocarbon Phase Prediction? AAPG Search and Discovery, #42513

Murray A., Dawson D.A., Carruthers D. and Larter S. (2013) Reservoir Fluid Property Variation at the Metre-scale: Origin, Impact and Mapping in the Vincent Oil Field, Exmouth Sub-basin. Proceedings of the Western Australian Basins Symposium, Petroleum Exploration Society of Australia, Perth, August 2013 (A PDF is available from the author on request).

Oudot J. and Chaillan F. (2009) Pyrolysis of asphaltenes and biomarkers for the fingerprinting of the Amoco Cadiz oil spill after 23 years. Nature Precedings. 4. 10.1038/npre.2009.2975.1

Peters K. E., C. C. Walters and J. M. Moldowan, 2005, The Biomarker Guide: Cambridge University 479 Press, Cambridge, U.K., 1155 p.

Snowdon L.,  Volkman J.K., Zhang Z., Tao, G. and Liu, P. (2016). The organic geochemistry of asphaltenes and occluded biomarkers. Org Geochem., 91, 3-15.

Composition Fractionation During Petroleum Migration

By Zhiyong He, ZetaWare, Inc.

One of the goals of petroleum system modeling and analysis is to predict fluid composition and properties (GOR, API gravity etc.). However, most of the work in the past has been focused on the generation process, with compositional kinetics, etc. Below I will try to show that the petroleum under goes significant changes in composition and properties along the migration pathways due a number of secondary processes not well understood yet.  Most people are familiar with the Gussow (1954) migration model in the figure below. The trap closest to the kitchen would receive the latest, and most mature and therefore lighter fluid, which displaces less mature fluid to traps up dip. 

Fig. 1. Differential entrapment of petroleum along migration path (Gussow, 1954). Late forming gas displaces oil to up dip traps. 

Even without forming gas caps, the later fluid tends to reach the crest of the trap because it is lighter and more buoyant. This pattern is generally true in most basins. Oils with lower gas oil ratios, and lower API gravities are found further away from the generation kitchen. Closer to the kitchen, lighter fluids, sometimes gas condensates are found. 

There are a couple of other factors not obvious from the Gussow model. When the migrating fluid reaches bubble point, a separate gas (vapor) phase starts to form, as shown in the trap in the middle. The gas in the gas cap selectively dissolves the lightest fraction of the liquid as condensate. The remaining oil in the leg retains the heavier part of the incoming fluid. The physical properties in a dual phase trap would over time equilibrate to profiles shown in the figure below. 

Fig. 2. Properties of fluid in a dual phase trap under thermodynamic equilibrium. Red and green lines are reservoir pressure of the gas phase, and oil phase respectively. The blue dashed lines show both phases are undersaturated away from the gas oil contact. GOR and API gravity both decrease with depth, in both phases. 

The dashed lines are bubble point pressure (Pb) and dew point (Pd) pressures. The oil near the oil water contact is always the least saturated with gas, lowest in GOR and heaviest in gravity, as is the the oil that spills from the trap to the next. If the trap is leaking from the crest, the next trap above will receive a gas with lowest condensate content. 

Phase separation happens due to pressure drop below saturation pressure, so it happens along the migration path as well as in traps. If it happens along the migration path, the gas would gradually "bubble" out from the migrating oil phase and either get stuck along the migration pathway as residual saturation (migration losses), because relative permeability for the minor phase is much lower or zero, or trapped in small traps below seismic resolution, along with the light ends of the oil fraction (condensate) dissolved in the lost gas.  The remaining oil will have less solution gas, and become heavier, gradually.  

Even in single phase traps, not only the late arriving lighter fluid goes to the top and displaces the heaver fluid to the flank due to gravity (charge disequilibrium). Gravity segregation and thermal equilibrium may enhance or alter the composition profiles. The figure below shows some observed GOR and API gravity profiles in single phase reservoirs in different basins. 

Fig. 3. Fluid property (API gravity and GOR) profiles in single phase reservoirs, plotted against depth below crest of the trap. Both API gravity and GOR decreases toward the oil water contact.

Significant grading occurs in near critical fluids, as show in figure (c) on the right. These profiles are controlled by complex migration and filling process and PT history and some not well understood thermodynamic processes. Therefore we do not yet have the ability to predict the composition and properties of the fluids quantitatively during the migration process. There are also other secondary processes such as mixing, methane diffusion, water washing, stripping by non-HC gases, biodegradation that can significantly alter the fluid properties. 

In the previous post below. I discussed an alternative "top down" approach to provide a probabilistic estimate of the fluid type and properties in a given prospect.   

Select references:

Gussow, W.C., 1954. Differential entrapment of oil and gas - a fundamental principle. American Association of Petroleum Geologists, Bulletin 38, 816-853

Zhiyong He, and Andrew Murray, 2020.  Migration loss, Lag and fractionation: Implications for fluid property prediction and charge risk. AAPG annual conference, Houston Texas, Sept 28-30, 2020.

Gas Oil Ratio Trends In Sedimentary Basins & PVT Behavior

By: Zhiyong He, ZetaWare, Inc.

Gas oil ratios of oil and gas fields plotted against depth show interesting trends as shown below. The figure on the left is from large global datasets, and the one on the right is from an area in the North Sea. What are the reasons we may ask?

We have recently talked about this in several presentations (see references below). We concluded that this is a result of PVT behavior during migration. At shallower depth, the pressure is lower, and oil cannot dissolve as much solution gas as it can at a deeper depth. Likewise, gas can not dissolve much liquid at shallow depth.

This is supported by the relationship between saturation pressure (Psat) and GOR relationship based on some large PVT databases.

In this figure above, the blue shaded area are based on thousands of saturation pressure (bubble point on the left and dew point on the right) measurements. As HC generation windows are typically deeper than the blue band, migrating fluid toward shallow depth will reach saturation pressure at different depth depending on initial GOR of the fluid coming from the source rock. But once the Psat is reached, GOR will be limited by Psat, and follow the trend of the Psat-GOR relationship, resulting the distribution in figure 1.

This process not only changes GOR significantly from the initial fluid expelled from the source rock, it will also change the composition and API gravity. Below is a local example from a gas condensate system.

The initial fluid is found in a deeper reservoir (1) close to the kitchen, it is undersaturated as reservoir pressure is higher than initial Psat. In shallow trap along the migration path, the fluid is separated as a gas cap and an oil leg (2) and (3), with very different GOR and liquid API gravity. The fluid can further fractionate depending on whether migration is vertical or lateral, (4) and (5). Please also note that the saturation pressure itself is also modified by the same process, and becomes lower at shallow depths.

The same happens without a trap, or in between traps, along the migration pathway. In a gas condensate system like the above, the liquid phase that drops out is a) the heaviest fraction of the liquid first, and b) as droplets that are unable to form a continuous phase to migration along with the main gas phase.

Similarly, if the generated fluid is mainly oil, the GOR of the oil will follow the bubble point side of figure 2. Gas bubbles gradually drop out, or trapped in small traps that spill the liquid, reducing GOR along the way. As the gas phase that was dropped out retains the lightest ends extracted from the oil, the API gravity of the remaining oil decreases approaching shallower traps.

In any given trap, the HC fluid composition and therefore properties are not only a function of the initial generated fluid, but also on the pressure history and the complexity of the migration paths. The self regulating process of changing composition and in turn Psat itself, is much too complex to model at this time. Attempt to predict reservoir fluid properties solely based on source rock kinetics, as you may find in recent basin modeling literature, is misdirected in our opinion. A top down approach based on analyzing observed fluid properties in traps and trends in the geological context (Top Down PSA) is recommended.

Select References:

He, Zhiyong, and Andrew Murray, 2019, Top Down Petroleum Systems Analysis and Geospatial Patterns of Petroleum Phase and Properties. Celebrating the life of Chris Cornford (1948-2017): Petroleum Systems Analysis ‘Science or Art?’ The Geological Society, 24 - 25 April 2019

He, Zhiyong, and Andrew Murray, 2019, Top Down Petroleum System Analysis, Exploiting Geospatial Patterns of Petroleum Phase and Properties. AAPG Annual Convention, San Antonio, May 19-21, 2019 Download pdf from search and discovery

Murray, Andrew, and Zhiyong He, 2019, Oil vs. Gas: What are the Limits to Prospect-Level Hydrocarbon Phase Prediction? AAPG Hedberg Conference, The Evolution of Petroleum Systems Analysis, Houston, Texas, March 4-6, 2019 Download pdf from search and discovery

Zhiyong He, and Andrew Murray, 2020.  Migration loss, Lag and fractionation: Implications for fluid property prediction and charge risk. AAPG annual conference, Houston Texas, Sept 28-30, 2020.

Biodegradation Much? Common Wisdom vs Statistics

By: Zhiyong He, ZetaWare, Inc.

Many studies have shown that biodegradation can have significant impact on oil quality (eg. Larter et al, 2006, Yu et al 2002, Wilhelms, et al 2001). Peak degradation rates are around 30-40 degrees Celsius, which is roughly at about 1000 meters below mudline on average. How much is the risk (% probability) of finding heavy oil if we have a prospect at this depth? For practical purposes, lets say heavy oil means an API gravity lower than 20 API. This question was posted on LinkedIn as a poll, and the answers are anywhere between 10 to 90%, and the mode is around 70%. See the original post here  and many thanks for all who participated. 

Many of you know Andrew Murray and I have been working on examples and methods for Top Down PSA for the last few years. While looking for field/fluid data, I came across a paper titled "Properties of crude oils in Eastern Hemisphere" by Kraemer and Lane 1937. Having read the papers on biodegradation and developed a tool for modeling biodegradation in Trinity a while back, my first thought was that by 1930s the wells were probably very shallow and that many of them would be heavy oils. I was only right about the depths. It was very surprising that out of the 142 fields, less than 10% (13) had an API gravity of less than 20, as shown in the figure below.

The next paper I found was McKinney et al. 1966, which included fluid properties of 546 oil fields in the United States. The API gravity depth plot on the left shows the typical trend, that API in general decrease to shallower depth (Similar to figure 2, Larter et al, 2006). The figure on the right is the 359 fields shallower than 2000 meters. Only 18 (5%) of those are below 20. You can see most of the heavy oils are from California. Most of them are probably sourced by the well known Monterey Fm, which belongs to organo-facies A, perhaps that is (at least partly) the reason for the low gravity (and often high sulfur). Texas and Louisianan have a lot of shallow fields but have no oils below 20. Reservoirs formation of some of these outcrop at surface not too far from the fields.   

Next I plotted a global data set of ~16,000 fields that are less than 2000 meters deep. 14% of the top 1000 meters are less than 20 API, and only 7% of those between 1000 to 2000 meters. The figure on the right include the deeper fields as well.

So what does this all mean? Globally the base rate of heavy oil at shallow depth where biodegradation is a concern is only 10%. If we were to only rely on a basin model that includes the biodegradation process, we are much more likely to predict a heavy oil at these depths.

It is possible that such field databases may not include some discoveries where oil is too heavy to be produced (therefore not counted).  But I don't believe that is a significant enough number to change the statistics because this is such a large dataset, and if it is a prevalent problem there would have been a lot of literature on it. Note that some of the large heavy oil pools are included such as the Athabaska, Orinoco, Rubiales and Kern River.

We are aware of other factors that may prevent biodegradation - such as OWC configuration, nutrient supply,  paleo-pasteurization, and timing of charge (duration of oil in reservoir), etc. Most of these are very hard to determine. The statistics above would imply the possibility that one or some of these factors are very prevalent in most basins. My own suspicion is that in in vast majority of cases/basins charging of shallow reservoirs are active at present day, due to migration lag regardless of when generation occurred.

The most important take away from this is that we should always check base rate (Bayesian analogs) when using basin modeling (bottom up) to predict fluid properties in prospects. Our models only include a small fraction of physical/chemical processes that happen in nature and much of the input of these models are assumptions due to lack of data, and lack of understanding. 

Select references:

Wilhelms, A., S. R. Larter, I. Head, P. Farrimond, R. di Primio, and C. Zwach, 2001, Biodegradation of oil in uplifted basins prevented by deep-burial sterilization: Nature (London), v. 411, p. 1034– 1037.

Yu, A., G. Cole, G. Grubitz, and F. Peel, 2002, How to predict biodegradation risk and reservoir fluid quality: World Oil, April, p. 1– 5.

Larter, S. R. et al. 2006, The controls on the composition of biodegraded oils in the deep subsurface: Part II-Geological controls on subsurface biodegradation fluxes and constraints on reservoir-fluid property prediction. AAPG Bulletin, v. 90, no. 6 (June 2006), pp. 921–938.

Kraemer A. J. and E. C. Lane, 1937, Properties of typical crude oils from the fields of the eastern hemisphere. Department of the Interior. United States Government Printing Office. 

McKinney C. M. E. P. Ferrero, and W. J. Wenger, 1966. Analysis of crude oils from 546 oilfields in the United States. Bureau of Mines. Untied States Department of the Interior. 

Maximum Seal Limited Hydrocarbon Columns

If a trap has a large enough closure height, the capillary top seal becomes the limit of the oil column height trapped when available charge is sufficient. The maximum column height, Ho, is given by the capillary equation: 

where  ρw and ρo are densities of water and oil respectively. γo is the interfacial tension between water and oil, θ the contact angle, g the acceleration of gravity and r the pore throat radius of the seal.  In the case of a gas only column, one can simply substitute the subscript o with g, replacing the density and interfacial tension for gas. Since subsurface gas density is typically 1/3 to 1/2 of oil density, and γg is 1.5 to 2 times γo, the maximum gas column is about 20% to 30% smaller than for an oil column.

Under dual phase (gas cap over an oil leg) conditions, because γg is higher than γo, the capillary force against gas at the crest is stronger than that against the oil column at the GOC for the same pore throat radius at base of the seal. This leads to a combined maximum column larger than the maximum oil only column, as the gas cap cannot be completely leaked off. 

At equilibrium, the capillary force, Pcg, at the crest is balanced by the buoyancy of the combined column:  

         Pcg = 2· γg · cos(θ)/r = Hg· g· (ρw-ρg) + Ho· g· (ρw-ρo)

while at the GOC, the capillary force, Pco, is balanced by the oil column: 

          Pco = 2· γo · cos(θ)/r = Ho· g· (ρw-ρo)

Combine the two equations and canceling out r and cos(θ), we have:

Under typical reservoir conditions, this results in a gas cap that is about 1/6 to 1/5 of the oil column. 

The implication of this is that small gas caps may occur more frequently in large structures than we expect otherwise, as long as it is a dual phase system. This can also explain stacked pays that have gas caps at more than just the top reservoir. The Kikeh field in deep water Malaysia may be such a case. The "gas chimney" above the field, as well as the multiple pays indicate top seal control of the columns. Several of the stacked reservoirs have a small gas cap.  

Even if the seal can support an oil column larger than the trap closure, gas cap over oil leg can still be the case as long as it cannot also support a full gas column, as described by my earlier post.

Using Hydrogen Index as Maturity Indicator

The common practice in the oil industry is to make source rock maturity maps in terms of vitrinite reflectance (%Ro). However, vitrinite reflectance does not actually tell us to what degree the source rock has converted its generation potential to hydrocarbons. VR is merely a thermal stress (the combined effects of temperature and time) indicator, and a very poor one at that. To know how much of the kerogen has converted to hydrocarbons we not only need to know thermal stress, but also the kinetic behavior of the source rock, which depends on the organo-facies (Pepper and Corvi, 1995).    

This figure shows the fractional conversion (transformation ratio) of kerogen of different organo facies as a function of vitrinite reflectance (thermal stress). We see at 0.8%Ro, each of the standard kerogen facies has experienced very different degree of conversion, 70%, 60%, 40%, 20% and 0% respectively. 

Vitrinite Ro measurements are also not reliable and affected by many things, insufficient readings, suppression due to deposition/diagenetic environments (arguable by pressure as well), subjectivity and experience of the lab personnel, recycled sediments, samples from cavings, etc. In some marine environment, vitrinite macerals are very rare, and in older basins it simply does not exist.

I would like to recommend that we take a good look at one of the most commonly available measurements, hydrogen index (HI), as a maturity indicator. HI decreases from its initial immature value gradually to zero as the kerogen is converted to hydrocarbons. It is a direct measure of how much of the potential of the kerogen has left yet to be converted. Obviously initial values can vary from source rock to source rock, and even within a single source rock facies, but most of that can be filtered out by removing samples with low TOC, and by removing the lower values at each depth/location, as we typically have abundance of samples. This works very well in case of good marine source rocks, (most of the unconventional areas in the US), and especially at higher maturities.

Below is an example of mapping maturity using hydrogen index. This is the Bakken formation in the Williston basin. The color variation based on hydrogen index clearly shows the decrease of HI toward the deeper part of the basin. But the shape of the maturity window do not conform exactly to depth contours as the two more mature areas are also affected by thermal anomalies. 

     

There are several advantages of using HI as a maturity indicator. Most importantly, it is a direct measure of conversion, so it accounts for the effect of kinetics. Two different source rocks may require different thermal stress to get to the same transformation, but we know exactly how much is left. Most good marine source rocks starts off with an initial HI of about 600 mg/gTOC, so we we see 300, the conversion is about 50%, and when we measure 50, we have over 90% conversion. Secondly, it works well where Ro data is poor or absent - in very rich source rocks, in carbonate source rocks, and old source rocks. It is abundant, inexpensive. The instruments are very accurate and consistent. There is no subjectivity involved.   

The limits of oil vs gas prediction and the relationship to migration range and charge risk

The description of a forthcoming specialist conference on basin modeling includes the text:

BPSM (Basin and Petroleum System Modeling) has become an indispensable tool in frontier basins to identify risk, reduce uncertainty, and identify new potential areas. This technology has become more important over time as a result of increased understanding of processes and the rapid development of computing power. Both the hardware and the software are evolving to quantify more complex processes.  See here

One could only assess the veracity of the first part of this statement by carrying out a survey of companies to see how many use basin modeling as part of their evaluation process and how many consider it "indispensable".  What I think can be said is that, if basin models are "identifying risk and reducing uncertainty", then that isn't showing up in exploration success rates. Industry surveys show that frontier basin success rates have not changed much over the last 20 years, remaining less than 10% for a commercial discovery. I would also dispute whether the ability to "quantify more complex processes" has made a difference - increasing the complexity of a model does not mean increased predictive power. In fact, often the reverse is true because of a greater tendency to fit the "noise" in the system rather than the "signal" (see Nate Silver's excellent book "The Signal and the Noise: The art and science of prediction")

Some of us think that the lack of improvement in the predictive power of basin models is because they only partly address the two things most affecting the chance of a prospect receiving charge: The kitchen yield in relation to the volume of the migration pathway to the trap and the interaction of trap closure height and seal capacity (it doesn't matter whether we are speaking of fault seal or top seal). This is a topic that will be taken up elsewhere but of note are the presentations and papers of Richard Bishop (e.g. Bishop et al., 2015) and two other entries in this blog on traps being filled/not filled and traps leaking and spilling at the same time (in relation to the latter, see also the paper by Sales et al. 1997).

I would like to highlight one other aspect of this discussion: the controls on the occurrence of oil or gas in a trap and our ability (or lack thereof !) to predict it. The intrinsic link between trap fill and phase has already been discussed by Bishop (2015) and Sales et al. (1997). However, in Sales et al. (1997) excess supply of both oil and gas is assumed as precursor to the discussion. Bishop (2015) considers that such excess is implied by the observation that nearly all traps are filled to their spill or leak point. I would argue that not only the total amounts of gas and oil are important here but their relative amounts, i.e, the gas to liquids ratio of the incoming fluid. This, together with the pressure and temperature of the trap and the mutual miscibility of the gas and oil (dependent on their compositions), determines whether the fill of any individual trap is single or dual phase.

Firstly, let's look at the relative masses of oil and gas expelled from the standard Pepper and Corvi (1995) source rock types (cumulative):

Although maturity is often thought of as the strongest control on the amounts of oil and gas expelled by a kitchen, source rock type is a stronger control within most of the maturity range. Furthermore, the amounts of oil and gas retained in the source rock vs. expelled has a major impact on expelled fluid gas to liquids ratio (GLR):

With the default P&C (1995) retained oil and gas amount settings (100 mg/g/TOC and 20 mg/g/TOC respectively) a marine clastic (B) kerogen expels a fluid with GLR of ~ 1100 scfs/bbl at 50% kerogen conversion and ~ 2200 scfs/bbls at full conversion. The GLR for fluvio-deltaic source rocks is very sensitive to the hydrogen index input chosen but for the standard kerogen is ~ 4400 scfs/bbl at 50% and 8800 scfs/bbl at full conversion (as a point of reference, the system-wide GLR for the Taranaki Basin of New Zealand is ~ 10,000 scfs/bbl). 

Note that source rock type and expulsion/retention settings are INPUTS to basin models not OUTPUTS, so we can already see that basin modelling per se may not be good at predicting GLR

What happens when we put these fluids into a migration system (the culmination of which is our target trap) ? First lets look at how the mass/volume of oil vs. gas translates into phase and for this we need to use some standard bubble point and dew point curves: the ones in the diagram below are for UK North Sea oils and gases based on empirical observations (Glaso, 1980, England et al. 2002). There are many factors which affect the position and shape of these curves but that is a topic for another day and they are reasonable for our present purposes. The figure shows how the GLR at 50% kerogen conversion sits in relation to these curves for the P&C (1995) kerogen types:

The symbols here show the phase state of fluids in traps at different depths (assumes hydrostatic pressure) and the black bars highlight the intersection with the dew point/bubble point curves.

If we charge our system from a standard "B" type source (50%) conversion and all those fluids arrive in a trap, we can expect it to contain monophase oil if deeper than about 3100m and dual phase oil and gas if shallower than that. On the other hand, if our charge is from a standard "D/E" source all traps shallower than about 5100m would contain dual phase fluids. If we have a very gas prone type F (upper flood plain or paleozoic coals for example) we will hardly ever encounter anything other than gas. Similarly, if the source is a very oil prone lacustrine "C"  or marine carbonate "A" (not shown in the figure) we will find mostly oil filled traps. Once again there are factors such as migration lag and in-trap alteration which will modify these conclusions in specific circumstances. However, their generality is borne out by the relative frequency of oil vs. gas discoveries in petroleum systems driven by one of the end-member source types. As examples one may cite the oil dominance in offshore Angola or the Bohai Basin of China (C type source) and the gas dominance on the outer Exmouth Plateau of Australia (F type source).

Now let's see how this plays out in a migration plumbing system. The diagram below shows a stylised series of three stacked reservoir/seal pairs with the top seal capacity varying both vertically and laterally for reservoirs 2 and 3 as shown. The actual values are not important here - it is the closure height to seal capacity ratio which matters - but the seal capacity does increase with depth as we might expect as the rocks compact. We are going to inject fluids with varying GLR into the base of the system (this whole exercise is done in Zetaware Trinity). 

For example, if we inject enough of a fluid with a GLR of 3000 scfs/bbl it will begin to migrate vertically at the second trap up-dip and then laterally within reservoir 2 where it leaks again at the most up-dip trap to reach reservoir 3:

Here are the patterns of oil and gas obtained with varying input GLRs (nb: input GLR varies from chart to chart but is held constant during the migration fill process):

Note that we change from expressing GLR as a GOR (scfs/bbl) to a CGR (bbls/MMscf) once it exceeds 3000 scfs/bbl.

We can note several things from this:

1. At low input GLR gas does not displace oil up-dip: it can't do so if the system remains single phase
2. At very high input GLR we do not drop out an oil rim at any realistic depth. However for gas condensates with CGR of about 50 bbls/MMscf or higher oil rims do begin to drop out and may even lead to oil filled traps (the oil found here would be saturated with gas). Commercial oil pools can be (and are) found in dew point systems - although they may also sometimes be present as "nuisance" oil rims to commercial gas pools. The distribution of oil and gas in traps can be complex in all but the most oil or gas dominated systems
4.  Discovering an oil or gas pool or even several does not necessarily define the system as "oil prone" or "gas prone". Compare the patterns of oil and gas occurrence for the 3000 scfs/bbl and 50 bbls/MMscf (= 20,000 scfs/bbl) input cases in the figure. This has not stopped some frontier basins with one or two oil or gas discoveries being labelled as "gassy" or "oily". In reality, a close look at the fluid properties and geochemistry is needed to make this call.

Next let's see what happens when we have a more realistic charge scenario, with the input GLR increasing as maturity of the source increases:

This is for a standard P&C type D/E source rock varying in maturity from a vitrinite reflectance equivalent of 0.85% to 1.6% Ro. At low to moderate maturity the trap fill is dominated by oil but volumes are also low so that only the first few traps in the migration system receive charge (in many cases we will never find these pools because they are deep and with low gas content will not have associated seismic DHIs).

There is naturally more gas in the migration pathway as the source matures. However, notice that even at maturities above 1.3% Ro (the conventional "top gas window") it is possible to find oil. We might, for example, drill the middle trap, find that it contains gas or oil+gas and then deepen the well to find oil. Again, the decision about what to do should hinge on what the fluid property and geochemistry data for the first discovered fluid tell us about the petroleum system. The highest proportion of oil containing traps occur when the source is low mature but this also means fewer trap overall have received charge. If only oil is commercial in our area of interest, we trade off reduced phase risk against an increased risk of finding nothing at all.

This raises the question of charge sufficiency: Bishop (2015) observes that charge is not the limiting factor for trap fill even in systems apparently charged by lean source rocks.  I suspect that the source rock quality and yield has been underestimated in many of these "lean" source rock cases because the true source - often deep in the kitchen - has never been drilled. This would explain why some of the data of Sluijk and Nederlof (1984) represent instances where more hydrocarbons were found in traps than were generated in the corresponding kitchen.

Studies such as those of Sluijk and Nederlof (1984), Biteau et al. (2010) and others cited by Bishop (2015) suggest that the supply of HCs to a trap may commonly be 1 - 2 orders of magnitude higher than the amount needed to fill it. However, we cannot conclude from this that charge sufficiency for an individual trap is never a problem: The next figure shows the distribution of oil and gas in our artifical migration pathway for scenarios in which the kitchen expels 28, 57 and 115 mmbboe/km2. For the purposes of this example we assume no migration losses other than those required to fill each trap in the pathway. In reality, some hydrocarbons will also be lost in reaching the critical saturation threshold in the rocks around the source interval itself and in sub-seismic waste zones

In the low yield case many traps, including those we would be most likely to drill, never receive charge. Although basins without sufficient charge may be rare, for every basin there must be a point at which hydrocarbons run out - equivalent to the maximum migration "range". It might be further from the kitchen than we expect but it must exist. This should be thought of not as a sharp line (even though it is sometimes drawn that way on play chance maps) but rather as a zone of increased probability of drilling a dry hole (nb: this means drilling into an empty trap, not a partly filled trap, since this is statistically unlikely  - see http://petroleumsystem.blogspot.com/2012/08/probability-of-trap-not-filled-to.html).

It is also interesting to consider the impact of phase separation and where it occurs along the pathway: If vertical migration happens early in the sequence phase separation also occurs earlier and the volumetric expansion of gas with reducing pressure means that the same mass of hydrocarbons equates to a much larger volume. This in turn means a greater lateral migration range compared to situations in which most migration happens in deeper carrier beds.

Thus, source rock UEP can be thought of as a kind of "master variable" which controls not only the chance of finding a hydrocarbon filled trap but also - for mixed oil and gas systems particularly - the phase of hydrocarbons found in that trap. Furthermore, and again as discussed in other posts in this blog, UEP is a major control on charge timing. Hence, we see that many things we traditionally expect a basin model to tell us - the chance of a trap receiving charge, the timing of charge relative to trap formation, the phase state of the trapped HCs - are highly dependent on the inputs we choose for the source rock.

We can see also that the pattern of migration depends on top and fault seal capacity of each intermediate trap along the migration pathway: whether it leaks at the crest, leaks through fault juxtaposition or through a non-sealing fault plane. Have we any realistic chance of estimating this for a whole, three dimensional migration pathway (four dimensional if you also expect fault seal capacity to change over time )?  In his recent paper, Bishop (2015) discusses the inherent difficulty in determining whether a single trap is fill to the leak point, whether this is set by top or fault seal or by stratigraphic pinchout. I would add to this the observation that there have been many cases where the extent of compartmentalisation of discovered fields has been badly misread, even after extensive appraisal drilling. If we have trouble working out the plumbing of discovered and multiply drilled fields, what chance have we got of doing it for a whole migration pathway, especially since much of it will have, at best, coverage by 2D seismic ?

We can, I think, deal with this issue in several ways. Firstly, we can run multiple scenarios sampling the input space probabalistically or deterministically (or a combination as suggested by Bishop 2015). Secondly we can use our knowledge of compartmentalisation of discovered fields: There are several extant schemes or algorithms relating reservoir continuity to geological characteristics such as structural type, depositional environment, fault throw vs. net to gross, propensity for shale gauge etc. Nature is fractal so the same logic should apply to migration pathways: perhaps we can use such schemes to assign at least a relative efficiency to a migration pathway. Demaison and Huizinga (1994) referred to this with their low and high "impedance" systems but we can probably address the issue in a more detailed manner now, especially when we have 3D seismic attributes over some or all of the pathway.  I do not believe we can do it deterministically in basin models because we cannot provide such models with inputs of sufficient detail to define specific migration pathways.

Finally, it must be said that the migration "cartoons" used in this post to illustrate concepts take no account of the lack of mixing in many hydrocarbon pools. Calculations of in-reservoir mixing times (see Smalley et al. 2004 for example) suggest that they are often longer than the typical filling time. This was supported by the observations of Stainforth (2004) who argued that compositional grading of petroleum pools is the norm rather than the exception. My own experience includes fields which are clearly unmixed, as reported for the Forties Field (England, 1990) but also some that show remarkable homogeneity over large inter-well distances. The latter cases can arise when a trap has access to charge from multiple directions so that a natural "averaging" process occurs: different migration paths have different lengths and volumes. If we apply the same logic to the intermediate traps along a migration pathway it follows that the migration lag effect on fluid properties and phase - though a fundamental aspect of the migration process - may not always be significant in practice.

With this post I hope to have made the point that the prediction of phase  at the trap level is (a) fundamentally linked to the overall charge risk and therefore subject to similar uncertainties (b) inherently difficult in any mixed oil and gas charged petroleum system. I do not think this is a reason for pessimism or for not attempting to assign a phase risk to our prospects. Rather, given that it is hard to enough to find hydrocarbons in the first place - witness the low success rates in frontier basins - we should not worry about hydrocarbon phase at the trap level. If only one phase is likely to be economic we need to explore in basins where a dominance of that phase is likely, e.g. those likely to host very oil prone or very gas prone source rocks. Migration scenario testing can then help us home in on areas with the best chance of traps filled with the desired phase.

Once we are in a play or basin however, any hydrocarbon discovery is valuable, regardless of the phase: Examination of the fluids will tell us if we are in a fundamentally oil prone, gas prone or mixed system and guide our decision about what to do next - drill up-dip, down-dip, farm down or exit the play. Petroleum geochemistry has a major role to play here as compositional and isotope signatures exist for source type, relative maturity of expulsion, evaporative fractionation and secondary alteration by in-reservoir cracking, biodegradation and water-washing. All of these affect the GLR of trapped fluids.

All comments/criticisms etc. are welcome,

Rgds,
AM

References:

Bishop R.S. (2015). Implications of source overcharge for prospect assessment. Interpretation, 3, 93-107, AAPG

Biteau et al. (2010). The why and wherefores of the SPI-PSY method for calculating the world hydrocarbon yet-to-find figures. EAGE First Break, 28, 53-64

Demaison G. and Huizinga B. (1991). Genetic classification of petroleum systems. AAPG. Bull., 75, 1626-1643

England W.A. (1990). The organic geochemistry of petroleum reservoirs. Org. Geochem., 16, 415-425

England W.A. (2002) Empirical correlations to predict gas/gas-condensate phase behaviour in sedimentary basins. Org. Geochem., 33, 665-673

Glaso O. (1980) Generalised pressure-volume-temperature correlations. SPE 8016, 785-795

Pepper A.S. and Corvi P.J. (1995) Simple kinetic models of petroleum formation: Part 1: oil and gas generation from kerogen. Marine and Petroleum Geology, 12, 291-319 (see also part II and III of this series of papers)

Sales J.K. (1997) Seal strength vs. trap closure - a fundamental control on the distribution of oil and gas. In: Seals, traps and the petroleum system, AAPG memoir 67, 57-83

Sluijk D. and Nederlof M.H. (1984). Worldwide geological experienceas as as systematic basis for prospect appraisal. In: Demaison G and Murris R.J. eds. Petroleum geochemistry and basin evaluation. AAPG Memoir, 35, 15-26.

Smalley et al. (2004). Rates of reservoir fluid mixing: implications for interpretation of fluid data. In: Cubitt J.M., England W.A. and Larter S. (eds.) Understanding petroleum reservoirs: towards an integrated reservoir engineering and geochemical approach. Geol. Soc. Lon. Spec. Pub. 237, 99-113

Stainforth J.G. (2004). New insights into reservoir filling and mixing processes. In: Cubitt J.M., England W.A. and Larter S. (eds.) Understanding petroleum reservoirs: towards an integrated reservoir engineering and geochemical approach. Geol. Soc. Lon. Spec. Pub. 237, 115-132

See also the blog posts:
http://petroleumsystem.blogspot.com/2012/08/probability-of-trap-not-filled-to.html

http://petroleumsystem.blogspot.com/2012/07/can-trap-spill-and-leak-at-same-time.html