FLUID IDENTIFICATION SYSTEM AND PRODUCTION AND USE THEREOF

Abstract

A fluid identification system comprising a plurality of particles, each particle encapsulating therein at least one tracer material having an identifiable DNA, the at least one tracer material being encapsulated by an encapsulation material, wherein the particles are adapted to retain the at least one tracer material in an encapsulated form after exposure of the particles to a temperature of at least 75? C. and/or a pressure of at least 1000 psi (6.9?10.sup.6 N/m.sup.2).

Claims

1. A method of producing a fluid identification system, the method comprising the steps of: a. providing at least one tracer material having an identifiable DNA; b. complexing the at least one tracer material with at least one first polymer in a first solvent; and c. encapsulating the at least one tracer material complex in an encapsulation material comprising at least one second polymer to form a plurality of particles, each particle comprising encapsulation material surrounding the at least one tracer material complex.

2. The method according to claim 1 wherein the encapsulation step (c) is carried out in the liquid phase and the particles are formed as an emulsion in the liquid phase, wherein the emulsion comprises an aqueous phase in an oil phase.

3. The method according to claim 2 wherein the encapsulation step (c) is carried out by polymerising a polymerisable material in the liquid phase to form the plurality of particles which include polymerised material comprised in the at least one second polymer, each particle comprising the polymerised material encapsulating therein the at least one tracer material complexed with the at least one first polymer.

4. The method according to claim 3 wherein the polymerisable material includes monomers having water-soluble and oil-soluble groups.

5. The method according to claim 3 wherein in step (c) the encapsulation is achieved by formation of polymer-coated droplets by interfacial polymerisation in an emulsion.

6. The method according to claim 5 wherein in step (c) the polymerisation occurs at a liquid-liquid interface to encapsulate the at least one tracer material complexed with the at least one first polymer.

7. The method according to claim 1 wherein in step (c) the at least one tracer material complex is present in an emulsion of aqueous-phase droplets dispersed in an oil phase, the oil phase comprising a polymer or at least one monomer to form the encapsulation material by polymerisation.

8. The method according to claim 7 wherein in step (c) the oil phase comprises at least one monomer to form the encapsulation material by free radical polymerisation.

9. The method according to claim 7 wherein the oil phase includes a second solvent for the at least one monomer, the encapsulation material being substantially insoluble in the second solvent.

10. The method according to claim 7 wherein at least one of the oil phase and the aqueous phase includes a polymerisation initiator for polymerising the at least one monomer.

11. The method according to claim 7 wherein in step (c) the oil phase comprises at least one polymer to form the polymerised material surrounding the complex by cross-linking.

12. The method according to claim 11 wherein in step (c) the oil phase comprises at least one polymer to form the polymerised material surrounding the complex by precipitation from solution in the liquid phase.

13. The method according to claim 7 wherein in step (c) at least one surfactant is present in at least one of the aqueous-phase droplets and the oil phase.

14. The method according to claim 13 wherein in the at least one surfactant comprises at least one non-ionic amphiphilic molecule selected from a polyethylene oxidepolypropylene oxide copolymer, a polyethylene oxidehydroxyalkyl ester triblock copolymer, a sorbitan alkanoate, a sorbitan ester, a polyalkene anhydride, an alkoanol, an alkanoic acid, a sorbitan ester, an alkylpolyether, an alkyl alkylene oxide block copolymer, an alkyl-alkylene diol, or a mixture of any two or more thereof

15. The method according to claim 14 wherein the surfactant, the oil phase and the aqueous phase are present in a weight ratio of 5-30 wt % surfactant: 40-80 wt % oil phase: 2-55 wt % aqueous phase.

16. The method according to claim 1 wherein the encapsulation material comprises at least one acrylate-, methacrylate- or styrene-based polymer, a methyl methacrylate polymer, a vinylpyrrolidone polymer, a polyurethane polymer, a polystyrene polymer, a polyethylene oxide polymer, a polyethylene glycol polymer, an alkylpolyether polymer, or an epoxy polymer.

17. The method according to claim 1 wherein the particle is adapted to be degradable in order selectively to release the DNA therefrom for analysis.

18. The method according to claim 17 wherein the encapsulation material comprises a linear polymer containing degradable co-monomers or a cross-linked polymer containing degradable cross-linkers.

19. The method according to claim 18 wherein the encapsulation material includes a chemical grouping adapted to be selectively broken thereby to degrade the particle to release the DNA therefrom for analysis.

20. The method according to claim 19 wherein the breakable chemical grouping is an ester, urethane, carbonate, disulphide or amine group.

21. The method according to claim 20 wherein the breakable chemical grouping is a disulphide adapted to be reduced using a dithiothreitol (DTT) reagent thereby to degrade the particle to release the DNA therefrom for analysis.

22. The method according to claim 1 wherein the DNA of the tracer material is complexed with polyethylene imine, the molar ratio of nitrogen in the polyethylene imine to phosphorous in the DNA is from 5 to 30, the encapsulation material comprises at least one acrylate polymer, methacrylate polymer or methyl methacrylate polymer, the polymer of the encapsulation material includes a breakable chemical grouping adapted to be chemically reduced using a reagent, thereby to degrade the particle to release the DNA therefrom for analysis, and the encapsulation material has been polymerised in an oil phase by atom transfer radical interfacial polymerisation in a water-in-oil emulsion.

23. The method according to claim 22 wherein the breakable chemical grouping is a disulphide group.

24. The method according to claim 1 wherein the DNA of the least one tracer material is solubilised in the first solvent, the first solvent being an aqueous solvent.

25. The method according to claim 1 wherein the DNA of the least one tracer material is at a concentration in the solvent lower than a gelation concentration for the DNA in the solvent.

26. The method according to claim 1 wherein the DNA of the least one tracer material is at a concentration in the solvent of from 0.1 to 5 ?g/ml.

27. The method according to claim 1 wherein at least one tracer material complexed with at least one first polymer has a dimension of from 1 to 100 nm.

28. The method according to claim 1 wherein the at least one first polymer comprises a cationic or hydrogen bonding polymer complexed with the DNA of the least one tracer material.

29. The method according to claim 1 wherein the at least one first polymer includes a nitrogen-containing functional group complexed with the DNA, wherein the nitrogen-containing functional group is an amine group.

30. The method according to claim 29 wherein the at least one first polymer comprises at least one of polyethylene imine and poly-L-Lysine or a mixture of two or more thereof.

31. The method according to claim 1 wherein the at least one first polymer comprises nitrogen and the molar ratio of nitrogen in the at least one first polymer to phosphorous in the DNA of the least one tracer material is from 5 to 30.

32. The method according to claim 1 wherein the at least one first polymer comprises polyethylene imine and the molar ratio of nitrogen in the polyethylene imine to phosphorous in the DNA of the least one tracer material is from 5 to 30.

33. The method according to claim 1 wherein the particles are adapted to retain the at least one tracer material in an encapsulated form after exposure of the particles to a temperature of at least 75? C. and/or a pressure of at least 1000 psi (6.9?10.sup.6 N/m.sup.2).

34. The method according to claim 1 wherein the particles have an external dimension of from 50 nanometers to 500 nanometers.

35. The method according to claim 1 wherein the at least one tracer material is dispersed in a matrix of the polymerised material.

36. The method according to claim 1 wherein the at least one tracer material is contained in a cavity within a capsule of the polymerised material.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0061] Embodiments of the present invention will now be described, by way of example only, with reference to the accompanying drawings, in which:

[0062] FIG. 1 is a generalized workflow in accordance with an embodiment of the present invention;

[0063] FIG. 2 schematically illustrates a number of exemplary DNA identification spectra in accordance with a second embodiment of the present invention;

[0064] FIG. 3 shows a schematic illustration of the detection of fracture or other fluid which is in accordance with yet another embodiment of this present invention;

[0065] FIG. 4 schematically shows the detection of cross-flow as part of an EOR methodology which is in accordance with another embodiment of the present invention;

[0066] FIG. 5 schematically illustrates the detection of behind casing flow which is in accordance with another embodiment of the present invention; and

[0067] FIGS. 6A and 6B schematically illustrate, respectively, a nanoparticle manufacture process and a nanoparticle disassociation process in accordance with another embodiment of the present invention.

[0068] The foregoing will be apparent from the following more particular description of example embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating embodiments of the present invention.

DETAILED DESCRIPTION

[0069] Hereinafter, the present invention will now be described in more detail with reference to the accompanying FIGS. 1 to 6A-6B, in which exemplary embodiments of the invention are shown. The invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

[0070] Referring to FIG. 1 where a generalized workflow is shown that captures some of the embodiments of this invention. In a step 10, of the workflow, DNA with specific characteristics or signatures is encapsulated within nanoparticles which have the specific features that they are inherently stable at temperatures >100? C. and at pressures >5000 psi (>34.5?10.sup.6 N/m.sup.2) for long periods of time, typically >1 year. Encapsulation is achieved by use of formulation of polymer-coated droplets by carrying out interfacial polymerization in emulsions. This takes place at ambient conditions, so avoiding exposure of the DNA to high temperatures during encapsulation, with the size varied from nanometers to microns by choosing either (nano) emulsions or suspensions at the starting point. The coating is based on high melting methacrylate or styrene based polymers. A disulphide cross-linker is used to increase the solvent and thermal resistance of the coating. Moreover, the cross-links can be reduced under relatively mild conditions by e.g., dithiothreitol (DTT) reagents, which provides a means for selectively degrading the coating of the particles and so releasing the DNA. The release of the DNA is labelled as step 13 in the workflow in FIG. 1.

[0071] During oil and gas exploration, production and transportation operations many fluids are used or collected. Some of these fluids have special functions, for example, cleaning the wellbore to allow oil to easily flow. These fluids can be very expensive and in some cases quite dangerous to human health, e.g., acids. Therefore it is important to track them and ensure that they are used safely. In step 12 of the workflow, nanoparticles are added to these fluids. The DNA within the nanoparticles will contain a coding which allows each fluid to be uniquely identified.

[0072] The introduction of the nanoparticles into the fluids can occur at the well site as the fluids are pumped into the well or they can be added at the point of manufacture and so arrive at the well site already tagged with its unique identifier. Those skilled in the art will appreciated that adding these kinds of particles to the fluids can take place at many different places within the processes of exploration, production or transportation.

[0073] The particles will be added in very large quantities, e.g., on the order of 10.sup.10 particles, which because of their very small size will become entrained within the fluid flow becoming part of the bulk volume. For example, they will not settle as perhaps grains of sand would. They follow the fluids where ever it flows and this includes into the reservoir rocks themselves. Again because of their nano-size they will easily pass through the pore throats and fractures within the reservoir without blocking or impeding flow. This is a very important feature of this invention. In step, 10, particles are manufactured such that concentrations of ?10.sup.10 particles/liter are produced. Therefore, as many liters of fluid containing these particles can be added to process fluids as is required to provide the desired number of particles as needed to deal with, e.g., dilution as the process fluids flow through the system. Those skilled in the art will appreciate the volumes required depending on the fluids or operation that is being monitored.

[0074] It is also common practice for fluids to be collected during the various processes that occur during oil and gas exploration, production and transportation. These fluid samples can be collected at surface when fluids that are pumped into a well or wells returns to surface. Fluids can also be collected directly from the rock formations using specialist tools well known to the industry call logging or production logging tools. These instruments are lowered into the well and can draw fluids from the rocks into fluid-chambers in the tool itself. The captured fluids are pulled back to surfaced in the tool and the fluids can be sent to laboratories (either on the well site or elsewhere) in the fluid-chamber where it can be analyzed chemically and/or physically. It is also known that rock core samples can be obtained by use of specialist tools or during drilling/coring operations. These cores are brought to surface for analysis and again the fluids within the core or the material such as mud filtrate can be accessed at surface using standard procedures.

[0075] In the workflow of FIG. 1, in step 12 nanoparticles are collected from any fluids retrieved and broken to release the DNA enclosed and in step 13 the DNA is matched to known fluid signatures as described later. In one embodiment of this invention, magnetic nanoparticles are encapsulated with the DNA in order to facilitate the collection of particles using a magnetic field.

[0076] Those skilled in the art will appreciate that while ?10.sup.10 particles can be added to process fluids, modern techniques such as qPCR can make a reliable detection of specific DNA molecule sequences with use of material from just ?100-1000 particles. Therefore significant dilution is possible without loss of functionality. It should also be appreciated that a collected fluid sample can contain DNA particles from different source fluids. It is a feature of this invention that the relative number or ratio of DNA particles attributed to one process fluid compared to another can be used to estimate the concentration of the different fluids within the sample.

[0077] Referring to FIG. 2, six graphs are shown. It should be noted that the information on the graphs is purely illustrative in nature and they show the presence of specific DNA sequences as vertical lines or indications at specific points on the horizontal axis. It is appreciated by those skilled in the art that there can be many graphical or other ways to illustrate the presence or otherwise of specific DNA sequences in a sample, e.g., graduated colored bar-graphs etc.

[0078] In FIG. 2 is illustrated just one way which has been chosen in order to facilitate the explanation of embodiments of this invention. Each vertical line can be consider to illustrate the presence of a sequence and all the lines taken together can be used to illustrate the presence of a specific DNA signature. These plots will be used for explanatory purposes solely and, in fact, those skilled in the art will appreciate that such sequences and signatures may not even been seen as DNA matching can be performed in an automated fashion.

[0079] Returning to FIG. 2, reference numeral 20 shows a DNA signature which is unique. In this invention, the DNA is encapsulated as described in other embodiments within nanoparticles and introduced into a process fluid to uniquely identify it. Samples collected and which contain this DNA signature show that the source process fluid which was tagged with this unique DNA signature is present in the sample and without any doubt. In FIG. 2, reference numeral 21 shows a DNA signature of a second fluid which also has its own unique signature so that the two source fluids which have signatures 20 and 21 can be uniquely identified.

[0080] Therefore, it is an embodiment of this invention that any process fluid can be laced with DNA capsules which have signatures which are unique so that these process fluids can be individually identified during any operation in oil and gas exploration, production or transportation. Those skilled in the art will appreciate the value of such a feature and will see that there are numerous applications which are envisaged in this invention.

[0081] It is also appreciated that a DNA signature can be broken down into constituent sequences which can be used for further refinement of an identification schema. As an example, parts of the signature can be used to uniquely identify a manufacturer of a particular fluid as illustrated by reference numerals 22 and 23 in FIG. 2 where the pattern shown in reference numeral 22 identified one particular manufacturer and reference numeral 23 identifies a second manufacturer.

[0082] In one embodiment all manufactures of fluids will have their own specific pattern which uniquely identifies them. In addition, it is also possible to use another part of the signature to identify a particular type of process fluid. In FIG. 2, the element of the signature labelled 24 could be used to distinguish the fluid as a fracture fluid (as an example) and a different pattern as labelled 25 would identify the fluid as a stimulation fluid. In this illustration, the last part of the signature 26 would identify the specific formulation of the fracturing or stimulation fluids.

[0083] An industry wide catalogue of manufactures, fluid types and specific formulations can be developed. In some ways this is akin to members of a family having specific features of their DNA which identify them as a family member and other features which identify them as unique individuals.

[0084] Those skilled in the art will appreciate that what is described in FIG. 2 is a limited set of examples which clearly defines the concept captured in this invention and that many different embodiments of this concept are possible. These other embodiments are within the scope of this invention. Another example could be to group fluids that are pumped into a specific reservoir rock (or layer) with its own unique part of the signature. In this case, if one of these process fluids is detected in some other part of the reservoir then it must have arrived there through the rock formations or through leak paths in the well system. Some of these examples will be described with the aid of FIGS. 3?5 below.

[0085] FIG. 3 shows a simplified schematic of the flow of fracturing fluid in a horizontal well that has been drilled into a formation 38 which could be, for example, gas shale. Gas shales are particular reservoir rocks which have very low permeability such that gas does not flow through them very well. In order to produce gas from them it is generally necessary to fracture the shale so that flow-paths are created for the gas to flow back into the well. In this example, a casing 30 is cemented into place and has been perforated with perforations 32 at some specific locations. Inner tubing 31 has been run inside the casing 30. A means to communicate 311, (e.g., a valve, not shown) fluids from inside the tubing 31 to outside the tubing 31, and vice versa, are provided. Also a means to isolate the particular zone of the casing 30 around the perforations 32 is provided using packers 33.

[0086] High pressure fracturing fluids 34 are pumped from surface down the tubing 31, through the valve 311, through the perforations 32 and into the formation 38. Because the formation rocks are of very low permeability and due to the very high hydraulic forces produced, the formation rocks fracture to create a network of fracture paths, 35A, 35B, 35C, 35D. These operations can require the pumping of significant volumes of fracture fluids, typically on the order of 100s of barrels per minute, and over long periods of time (many days). Proppants can be pumped into the fracture network to ensure they remain open for gas flow. The objective is to create a large fracture network 35A, 35B, 35C, 35D from which the gas can flow back to tubing 31 and to surface once the fracturing operation is complete and the well is put onto production. These operations are well known to those skilled in the art and can take many forms.

[0087] However, if during these operations the fracture network extends to an overlying permeable formation 36 as shown in FIG. 3, then leak paths 37 can be created and fracture fluid can flow thought the permeable zone. It is possible that an offset well 39, which could be a water well if the overlying permeable zone is an aquifer, can become contaminated. The illustration in FIG. 3 is quite simplistic but those skilled in the art can appreciate that the leak path(s) can be across many overlying/underlying formation rocks through natural fractures or faults in the rock.

[0088] In an embodiment of this invention, samples collected from offset wells or from the same well at different depths and nanoparticles captured as described in other embodiments, can be analyzed to determine the DNA signatures so as to determine if fracture fluids or any other type of processing fluid used during any operation, is present. The samples can be collected by any one of many methods that are common to the industry.

[0089] FIG. 4 shows yet another embodiment of this invention. This figure shows a schematic of an enhanced oil recovery (EOR) technique involving the injection of water into a reservoir rock in order to sweep oil towards a production well 43. In FIG. 4 there are two permeable layers of reservoir rocks 41. The lower layer 41 has oil present but its pressure is no longer sufficiently high enough to allow oil to flow 48 naturally to surface through the production well 43. An offset well 40, which could have started its life as a production well, is used to inject water down from surface 47 into the lower permeable layer. The water 45 enters into the layer and pushes the oil towards the production well 43. An interface 49 can be created whereby water exists to the right hand side and oil exists to the left hand side as shown in FIG. 4. However, if a fault or fracture 42 exists then a large portion of the injected water 45 can traverse the fault 42 up into the top permeable layer 41 along path 46. This results in a much smaller portion of the injected water flow 45 being available to push oil towards the production well 43. This is illustrated by the smaller arrow 44. In this is scenario the efficiency of the EOR process is much reduced and another method may need to be deployed.

[0090] Other scenarios could result in the injected water being channelled through a thin highly permeable lay in the lower reservoir rock 411, by-passing the oil in the layer and so resulting in very low sweep efficiency. However, technology available today makes it very difficult to detect these kinds of issues with any degree of accuracy.

[0091] One embodiment of the present invention uses the nanoparticles which contain a unique DNA signature to be injected with the injection water 47. If it is detected very early (early in this context could be months instead of years) in the production stream from 43 then it can be an indication of a high permeable zone by-passing the sweep. Or if it is detected in samples taken from the upper reservoir layers then it is an indication of cross-flow between layers. This information is of significant value to an operator of the field as EOR techniques can be modified or changed in order to optimize production from the field.

[0092] FIG. 4 shows some simplified examples, however, those skilled in the art will appreciate that there can be many other scenarios in which a unique fluids identification system as described in other embodiments of this invention can be used to detect and thus be used to optimize reservoir production.

[0093] FIG. 5 shows yet another embodiment of this invention which illustrates the identification of behind-casing flow. FIG. 5 shows casing 50 which has been cemented in place and is therefore enclosed in cement 51 which fills the gap between the wellbore wall and the outer surface of the casing 50. This cement 51 holds the casing 50 in place but also provides a seal so that reservoir fluids cannot flow up the annulus between the casing 50 and the wellbore. In FIG. 5, there exists a producing formation layer 56 from which oil is produced. An inner tubing 54, comprising production tubing, has a means, such as ports 52, to allow oil to flow from the casing 50 into the tubing 54. The oil flows from the reservoir layer 56, through perforations (not shown) in the casing 50 and through the communication ports 52, into the tubing 54 and up to surface for collection. The flow path is labelled 57. The annular zone between the casing 50 and the production tubing 54 is isolated by mean of the packers 53 shown in FIG. 5.

[0094] However, what is illustrated in FIG. 5 is that the cement 51 has not been put in place correctly or its formulation is not correct for the environment in which it is being used. As a result, a leak path or channel has developed which links the perforation zone with areas in the well above the packers 53. The path is illustrated by 55. This can be a dangerous situation as hydrocarbons now have a potential path up the well other than through the controlled path generated by the production tubing 54. Such an issue would require immediate remediation. However, it can be very difficult to identify such a leak path early as it could be very small and initially the flow through it can be difficult to identify.

[0095] In one embodiment of this invention, nanoparticles containing known and unique DNA signatures are pumped into the producing reservoir rocks, e.g., entrained in the fracturing or stimulation fluids. They can also be pumped and entrained in the cement 51 itself. Samples taken from the annulus between the casing 50 and tubing 54, in areas above or below the specific zone isolated by packers 53, are then analyzed so as to detect the presences of these unique DNA signatures. The detection of these unique signatures is an indication of cross-flow behind the casing 50 or potentially behind the packers 53. It is well known in the industry that packers 53 can be replaced or inflated to higher pressures in order to create the required sealing. If, however, the cross flow continues then it is likely it is occurring behind the casing 50 and a more involved remedial process is urgently required.

EXAMPLE

[0096] In the following section we provide a worked example. It is understood that what follows consists of process steps which might be performed in a different order than presented. It is also anticipated that those skilled in the art could substitute certain steps for others and/or omitted or modify certain steps and/or substitute certain materials for others which are similar in nature or that provide a similar functionality or result to those here described. The disclosed invention is therefore in no way limited by the details of the provided working example shown.

[0097] FIGS. 6A and 6B provide workflows or process flows to manufacture and disassociate the micro/nanoparticles previously described, respectively.

[0098] In FIG. 6A the process starts with biological tagging material such as raw DNA. This can be naturally occurring DNA material with a known signature or preferably synthetic or manufactured DNA of known characteristics or signature. The signature may have specific characteristics in order to follow a particular identification schema, examples of which are illustrated in FIG. 2. This DNA is labelled 600 in FIG. 6A.

[0099] A first preferred step is to create a physical protection of the DNA. For example one method uses cationic or hydrogen bonding polymers. This provides additional protection to the DNA during the process steps that follow. This step is labelled 601 in FIG. 6A and the resulting DNA complexes are labelled 603.

[0100] DNA complexes are prepared by mixing specific concentrations of encapsulating polymer and DNA in a suitable buffer. For example TE buffer is a commonly used buffer solution used in molecular biology especially involving DNA, used to solubilize DNA while protecting it from degradation. The mixture is left to equilibrate at room temperature for some specific time period. One example uses polyethylene imine (PEI) an encapsulating polymer, with the amounts of PEI and DNA selected so that the PEI nitrogen to DNA phosphorus ratio is between 1 and 60. Preferably a PEI nitrogen to DNA phosphorus ratio of between 5 and 30 is used. A particular working example uses a PEI nitrogen to DNA phosphorus ratio of 20. However other ratios could be employed in this invention.

[0101] Also, other polyelectrolytes could be utilized as the encapsulating polymer, for example, poly-L-Lysine or hydrogen bonding polymers such as polyethylene glycol. In this worked example PEI has been selected.

[0102] The minimum equilibration time is preferably between 1 and 120 minutes, more preferably between 5 and 60 minutes. However, greater or shorter times could be employed. The process is labelled 601 in FIG. 6A and the resulting DNA complexes are shown as 602 in the same FIG.

[0103] It has been shown experimentally using methods for DNA detection known to those skilled in the art, for example, gel chromatography, UV spectroscopy, or fluorescence spectroscopy, that there is no degradation of the DNA within the complex as result of the above processes or as a result of the processes that follow.

[0104] In FIG. 6A the next step in the workflow is to create a stable micro-emulsion of water phase droplets in the oil phase. Preferably this is a water-in-oil emulsion which is a thermodynamically stable micro-emulsion. Throughout the following example and through this invention, a nano-emulsion can substitute for a micro-emulsion depending on the size of the water phase droplets. The water phase contains the DNA complexes fabricated in the previous steps and described earlier. The amount of DNA complex can be varied to achieve a desired concentration of DNA in the final emulsion. Preferably a DNA concentration from 0.001 to 30 ?g/ml is used, the upper limit being set by the gelation limit of the particular DNA being used. More preferably a DNA concentration from 0.1 to 5 ?g/ml has been used. However, it is appreciated by those skilled in the art that any concentration up to the gelation point can be used. Here gelation is defined as the point at which the DNA complex solution becomes too viscous to spontaneously form an emulsion or to form an emulsion using methods known to those skilled in the art.

[0105] In order to achieve a stable micro-emulsion, there are 3 or more components that need to be mixed in the correct ratios. These are; surfactant(s), an oil phase which may subsequently be polymerized or cross-linked and the DNA/water phase.

[0106] Suitable surfactants are typically non-ionic amphiphilic molecules. Preferably they are polyethylene oxide (PEO)-polypropylene oxide (PPO) copolymers or PEO-hydroxyalkyl ester triblock copolymers. More preferably, surfactants such as sorbitan alkanoates or polyalkene anhydrides can be used. In addition blends of these and other surfactants with other co-surfactants surfactants, such as alkoanols, sorbitan esters or alkanoic acids, can be used. However, in this invention many other types of surfactants with similar characteristics or which provide the same results could be utilized such as alkylpolyethers, alkyl alkylene oxide block copolymers or alkyl-alkylene diols. In the specific example described here, the water phase consists of polyethylene imine/DNA complex (with an N:P ratio of 20 and DNA concentration 1 ?g/ml) in TE buffer.

[0107] The oil phase comprises, or optionally consists of, polymerizable monomers or co-monomers, optionally diluted by a suitable solvent. The solvent may be, for example, selected from alkanes, alkanols, or ketones, and is chosen such that it is a solvent for the monomers/comonomers but not for the resulting polymer. The monomers are selected to be capable to form an outer solid protective coating for the aqueous droplets containing the DNA complexes, created by interfacial polymerization at the water phase/oil phase interface in the micro- or nano-emulsion.

[0108] Monomers and co-monomers can be used which lead to any polymer which is hydrolytically stable under the temperature, pressure, pH and other relevant conditions of the application. For oil well and oil reservoir applications, the choice may be restricted to monomers which can be polymerized by free radical polymerization processes, such as styrene, methyl methacrylate, or vinylpyrrolidone. The polymerization initiator may be contained in either the oil phase or the water phase, preferably the water phase. For other applications, such as groundwater tracers, polyurethanes, epoxy polymers or similar polycondensation polymers may be suitable.

[0109] An alternative procedure for all applications is for the oil phase to comprise, or consist of, a solution of a polymer or mixture of polymers containing chemical groups which can be cross-linked to form a cross-linked polymer layer at the oil phase/aqueous phase interface. This process can be augmented or complemented by using polymer solutions which have a lower critical solution temperature (LCST) or upper critical solution temperature (UCST) which enables the polymer to precipitate from the solution by an increase or decrease in temperature respectively.

[0110] It is also preferable that chemically-breakable (by, for example, chemical reduction or hydrolysis) chemical linkages are also incorporated into the polymer chains. Possible groups include esters, urethanes, carbonates, disulphides or amines. Suitable linkages are groups which are stable under the application conditions (such as under the temperatures, pressures, pH and salinities typically found in oil and gas wells or reservoirs) but which can subsequently be preferentially broken by the application of a suitable chemical or physical trigger e.g. a chemical breaker, a change in pH, temperature or pressure, the exposure to light or radiation or to an electrical or magnetic field, or to mechanical stirring.

[0111] More preferably disulphide (S-S) bonds are incorporated into the polymer chains, which can be broken at some later stage by a suitable reducing agent so that the polymer layer of the capsule is readily broken on demand. In the worked example, S-S bonds are used; however those skilled in the art may consider using other bonds or means to allow the polymer skin of the capsule to be broken. The described example uses polymethylmethacrylate (hereinafter MMA) as the preferred polymer because it has very high temperature and mechanical stability characteristics. In addition, its formation by polymerization can incorporate disulphide bonds. However, other polymers could be deployed, for example, polystyrene, that provides equally suitable properties for use in this invention.

[0112] In the worked example the oil phase can consist of purely MMA. However, in some instances it is advantageous for the oil phase to comprise MMA plus a hydrocarbon or other suitable diluent. The example provided has used pure MMA and also MIVIA plus hexane up to 99% by weight of the oil phase. The use of 80% by weight hexane as a diluent for the polymer, such as MMA has been found to be particularly suitable. However, in accordance with the invention other hydrocarbons or diluents can be utilized and the ratio of MIVIA to diluent can be varied in order to provide the desired concentration of monomer in the mixture.

[0113] In accordance with the invention, different surfactants may be used, depending on the amount of MMA used or the type of diluent. For example, it has been found that when MMA was used purely as the oil phase a sorbitan alkanoate surfactant in hexanol was efficient in forming a stable micro- or nano-emulsion. Polyethylene oxide di-1,2-hydroxyoctyl decanoicacid triblock copolymer can also be used. However, when both MMA and hexane were used in the oil phase, a blend of polyisobutylene succinic anhydride and sorbitan ester (surfactant S) gave stable and polymerizable micro-emulsions.

[0114] It will be readily understood by those skilled in the art that there exists a significant number of commercially available surfactants and diluents that can be utilized in accordance with various embodiments of this invention.

[0115] The selection and mixing of the appropriate surfactant, water phase and oil phase is illustrated by the process labelled 603 in FIG. 6A.

[0116] In this example, it is preferable to mix the three components in the ratios 5-30 w/w % surfactant(s): 40-80 w/w % oil phase: 10-55 w/w % water phase, more preferably 8.3 w/w % surfactant(s): 66.7 w/w % oil phase: 25 w/w % water phase.

[0117] However, it will be appreciated by those skilled in the art that varying ratios can provide a stable emulsion with differing properties, for example, greater amounts of DNA complex or thicker layers of polymer after the interfacial polymerization has taken place during the next steps to be described later. For example, if a mix of sorbitan alkanoate/hexanol: MMA (oil phase): water phase is used then a stable emulsion is formed with the ratios 23.6 w/w % sorbitan alkanoate/hexanol: 74.2 w/w % MMA: 2.2 w/w % water phase.

[0118] The resultant stable micro-emulsion is labelled 604 in FIG. 6A.

[0119] The final step in the workflow used to fabricate micro/nanoparticles, as illustrated in FIG. 6A, is the addition of an initiator to trigger the interfacial polymerization process. This is labelled 605 in FIG. 6A.

[0120] There are many methods to achieve such polymerization in which breakable linkages are introduced into the polymer. Examples include but are not limited to: synthesis of copolymers of N,N-bis(acryloyl) cystamine (BAC) and MMA/styrene, synthesis of copolymers of allyl disulphide and MMA/styrene with V50 azo initiator and synthesis of copolymers of L-cystine and MMA/styrene. However in this example synthesis of MMA via micro-emulsion ATRP (Atom Transfer Radical Polymerization) has been chosen. It is understood that those skilled in the art may select another polymerization methodology to provide the same result and these other methods may be employed in alternative embodiments of this invention.

[0121] The synthesis of polymethyl methacrylate (MMA) via this route was chosen because ATRP is one method to introduce disulphide bonds (linkages) into the polymer. The polymerization occurs via formation of a radical on Bis[2-(2-bromoisobutyryloxy)ethyl]disulphide (on the carbon atom adjacent to Br in the compound as shown below) and since Br resides on each end of the compound, initiation occurs from both ends of the molecule. The formation of polymer is by itself an evidence of introduction of disulphide linkages since an ATRP initiation can occur only by formation of a radical on bromide and not at disulphide linkages.

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[0122] Therefore polymerization of micro-emulsions was carried out in this example using ATRP. Copper bromide, bi-pyridyl (Bpy) and bis[2-(2-bromoisobutyryloxy)ethyl]disulphide were used as the initiator system, labelled 605 in FIG. 6A. Copper bromide and bi-pyridyl were used to form copper complex and bis[2-(2-bromoisobutyryloxy)ethyl]disulphide was used to introduce S-S degradable links into the polymer.

[0123] The above describes an example workflow for the fabrication of nano- or micro-particles which incorporate DNA. However, this invention is in no way limited by the example provided and those skilled in the art may devise other workflows using the same or different materials to create nano- or micro-particles and these other workflows are within the scope of, and alternative embodiments of, this invention.

[0124] The process detailed in FIG. 6A can fabricate DNA nanoparticles which are numerous and can manufacture as many 10.sup.15 capsules per liter. They are inherently stable and can survive for very long periods of time, for example many years, in the environments found in oil and gas reservoirs. These nano- or micro-capsules or nano- or micro-particles can be deployed as described in other sections of this specification and as shown in the step labelled 11 in FIG. 1. Deployment can be into any oil and gas fluids systems used during the operations of exploration, production and/or transportation. They can contain DNA that has specific pre-defined signatures as illustrated in FIG. 2. The nano/microcapsules can be designed for and used in other fluid flow/tracer applications such as groundwater tracing, leak detection from agricultural wastes or landfills or industrial processes, and any general purpose fluid tagging applications where a resulting fluid is uniquely identifiable.

[0125] After introduction into a fluid system and after passing through that fluid system entrained in the fluid, the particles/capsules can be collected by any of the means described in other sections of this specification. Once fluid samples have been collected, the process of particle disassociation as shown in FIG. 6B is carried out. The objective is to release the DNA in order that it can be used for further analysis as described previously and thus providing a fluid identification and characterization of the fluid system under investigation. It should be noted that during the sampling process any background DNA can be destroyed before the particles are disassociated therefore ensuring that the only DNA present in the sample after disassociation is the DNA that was contained within the micro/nano particles.

[0126] FIG. 6B provides an example workflow or process, however, it will be understood by those skilled in the art that it is within the scope of this invention to modify this workflow or the materials used therein in order to achieve the same result. What is described in no way limits the disclosed invention to this particular example.

[0127] The starting point in the workflow is labelled 610 in FIG. 6B and represents a sample of fluid taken from the fluid system by any of the methods previously described or used in the industry. The sample can contain a certain number of nanoparticles (or microparticles) or capsules. The number will depend on many factors.

[0128] It is firstly required to collect or isolate these capsules from within the sample and remove the outer polymer coating. In this example, the coating consists of MMA incorporating disulphide bonds as described in the workflow or process illustrated in FIG. 6A and described above. One method to separate these capsules is to centrifuge the fluid sample. This is a method well understood by those skilled in the art. If magnetic material has been added to the capsules as described in other sections of this specification, then the application of a magnetic field can aid in this separation. However, there are other techniques that can be used to achieve this separation, for example, filtration or the presence of a specifically coated collection plate to which the particle are naturally attracted (for example, the attraction could be chemical or electrostatic) and all are within the scope of this invention. In this example, the addition of the reducing agent D,L-dithreitol (DTT) is used to break the disulphide bonds or links thus removing the MMA polymer layer and so releasing the DNA complexes as shown 612 in FIG. 6B. The step of centrifuging and the addition of DTT is labelled 611 in the same FIG. In addition, because the DNA is protected prior to this step, any background DNA existing in the sample can be denaturalized before adding DTT so that the only DNA that exists is that which is released during the particle disassociation steps here described.

[0129] The next step in the workflow or process releases the raw DNA from within the DNA complexes as labelled 613 in FIG. 6B. This must be achieved without damaging or denaturing the DNA. Preferably the steps labelled 611 and 613 in FIG. 6B are carried out at room temperature. In this example, polyaspartic acid sodium salt is used to release the DNA from within the complex. It has been shown using techniques known to those skilled in the art, for example, fluorescence spectroscopy or gel electophoresis, that naked DNA survivability is achieved through all steps described in FIGS. 6A and 6B.

[0130] The workflow illustrated in FIG. 6B represents a worked example of the step labelled 12 in FIG. 1. It has also been shown experimentally that the nanoparticles fabricated as shown in FIG. 6A survive the environmental conditions that they are anticipated to experience when passing through fluid systems used during the oil and gas operations of exploration, production and transportation, including those where the fluids pass through an oil and gas reservoir.

[0131] Once the raw DNA has been retrieved as outlined above, the DNA signature itself can be analyzed by off-the-shelf technology (not described herein) in order to identify signatures or characteristics in the raw DNA and to perform automated (or other) matching that in turn provides a fluids identification system as described in other sections of this specification.

[0132] For example, the matching can be performed against a known database of unique signatures providing details of, for example, the manufacturer of the fluid, the type of fluid, where the fluid was introduced into the process fluid system, how long the fluid has taken to pass through the system etc. The fluid system can be any type of fluid system used during the oil and gas operations of exploration, production and/or transportation as described in other sections of this specification.

[0133] Additionally the resulting better understanding of the said fluids system greatly enhances the ability of those skilled in the art to better manage the said oil and gas operations of exploration, production and transportation and therefore increase the value to the operator or owner or other stakeholders of the oil and gas reservoir and better manage the potential environmental impact of those operations as described previously.

[0134] In this detailed description several embodiments of this invention are described. They provide a detailed description of the concepts captured in this invention. However, it is by no means exhaustive and those skilled in the art will appreciate that other embodiments are possible which use the concepts described. These other potential embodiments cannot all be described but are however encompassed within the scope of this invention.