Method and apparatus for determining mud contamination of formation fluid
09759830 · 2017-09-12
Assignee
Inventors
- A. Ballard Andrews (Wilton, CT)
- Soraya S. Betancourt (Katy, TX, US)
- Andrew E. Pomerantz (Lexinton, MA, US)
- Soumyajit Mandal (Cambridge, MA)
- Yi-Qiao Song (Newton, MA)
Cpc classification
G01V3/08
PHYSICS
International classification
G01V3/08
PHYSICS
E21B49/00
FIXED CONSTRUCTIONS
Abstract
A formation fluid sample is analyzed using NMR spectroscopy to obtain a NMR spectrum. The NMR spectrum is then analyzed to find evidence of the amount of olefins present in the sample. The amount of olefins present in the sample can then be correlated to the level of contamination of the sample. In one embodiment, a .sup.1H chemical shift of between substantially 4.5 and 6 ppm is used to identify olefins present in the sample. In another embodiment, a .sup.1H chemical shift of substantially 1.9 to 2.1 ppm is used to identify olefins present in the sample. The NMR spectral equipment can be located uphole or downhole.
Claims
1. A method of characterizing a single formation fluid sample, the method comprising: subjecting the single sample to a spectral nuclear magnetic resonance (NMR) analysis to obtain a chemical shift spectrum; and determining a concentration of synthetic based mud (SBM) contamination within the single sample by identifying an indication of an olefin within the spectrum without reference to another sample.
2. The method according to claim 1, wherein identifying the indication of the olefin comprises locating at least one peak within the spectrum representing the olefin.
3. The method according to claim 2, wherein the spectral NMR analysis detects hydrogen nuclei and the spectrum is a proton NMR spectrum.
4. The method according to claim 3, wherein identifying the indication of the olefin comprises integrating under the at least one peak between about 4.5 and about 6 ppm to obtain an olefin total and dividing the obtained olefin total by a spectrum total obtained by integrating under all peaks in the spectrum.
5. The method according to claim 4, wherein the olefin comprises a plurality of olefins and the at least one peak comprises a plurality of peaks between about 4.5 and about 6 ppm.
6. The method according to claim 3, further comprising: adding a standard to the single sample prior to subjecting the single sample to the spectral NMR analysis, wherein identifying the indication of the olefin comprises integrating under the at least one peak between about 4.5 and about 6 ppm to obtain an olefin total and dividing the olefin total by a standard total obtained by integrating under a peak representing the standard.
7. The method according to claim 6, wherein the standard is tetramethylsilane (TMS).
8. The method according to claim 6, wherein the olefin comprises a plurality of olefins and the at least one peak comprises a plurality of peaks between about 4.5 and about 6 ppm.
9. The method according to claim 2, wherein identifying the indication of the olefin comprises locating a peak representing a chemical shift of a compound adjacent an olefin in the sample.
10. The method according to claim 9, wherein the peak representing a .sup.1H chemical shift of a compound adjacent a olefin is between about 1.9 and about 2.1 ppm.
11. The method according to 10, further comprising: adding a standard to the single sample prior to subjecting the single sample to the spectral NMR analysis, wherein identifying the indication of the olefin comprises integrating under at least one peak between about 1.9 and about 2.1 ppm to obtain an olefin total and dividing the olefin total by a standard total obtained by integrating under a peak representing the standard.
12. The method according to claim 2, wherein the spectral NMR analysis detects carbon nuclei and the spectrum is a .sup.13C NMR spectrum.
13. The method according to claim 12, wherein the at least one peak is located between about 110 and about 150 ppm within the spectrum.
14. The method according to claim 9, wherein the peak representing the chemical shift of the compound adjacent the olefin is at a chemical shift in a .sup.13C NMR spectrum located between about 34 and about 40 ppm.
15. The method according to claim 14, wherein the peak representing the chemical shift of the compound adjacent the olefin is at a chemical shift in the .sup.13C NMR spectrum located between about 39 and about 40 ppm.
16. The method according to claim 1, wherein the concentration of SBM contamination comprises at least one of a hydrogen percentage and a weight percentage.
17. The method according to claim 1, further comprising: prior to subjecting the single sample to a spectral NMR analysis, locating a tool downhole in a formation and obtaining the single sample.
18. The method according to claim 17, wherein subjecting the sample to a spectral NMR analysis comprises conducting the spectral NMR analysis downhole.
19. The method according to claim 18, further comprising: jettisoning the single sample downhole based on the concentration of SBM contamination.
20. The method according to claim 18, further comprising: storing the single sample in said tool based on the concentration of SBM contamination.
21. An apparatus for characterizing a single formation fluid sample, the apparatus comprising: a nuclear magnetic resonance (NMR) module for conducting a spectral NMR analysis of the single sample; and a processor configured to determine synthetic based mud contamination of the single formation fluid sample using the spectral NMR analysis without reference to another sample.
22. The apparatus according to claim 21, wherein the NMR module is part of a wellbore tool and the wellbore tool is configured to withdraw fluid from a formation.
23. An apparatus according to claim 22, wherein the processor is located uphole.
24. An apparatus according to claim 22, wherein the wellbore tool includes a chamber for storing the single sample.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
DETAILED DESCRIPTION
(7) Illustrative embodiments of the present disclosure are directed to methods and tools for determining a concentration of synthetic based drilling mud contamination in formation fluids using a nuclear magnetic resonance (NMR) spectrum. A synthetic based drilling mud (SBM) is defined herein as a drilling mud that includes olefins. In turn, an olefin is defined herein as a cyclic or acyclic unsaturated chemical compound that includes at least one unconjugated carbon-carbon double bond. Typical base fluids that are used in synthetic based mud are linear monoolefins, polyalphaolephins (PAOs), linear alphaolephins (LAOS) and/or internal/isomerized olefins (IOs). As explained above, drilling muds are used to facilitate drilling of a wellbore. Synthetic based drilling muds are often used instead of oil based muds (OBM) because the olefins of the base fluids in synthetic based muds are generally unstable and will readily break down into non-toxic components. Nonetheless, synthetic based mud contamination can adversely impact a compositional analysis of formation fluid. Thus, the concentration of synthetic based mud contamination within the formation fluid sample is valuable information that can be used to ensure analysis of formation fluids with low levels of contamination. Details of various embodiments are discussed below.
(8) A concentration of synthetic based drilling mud (SBM) contamination in formation fluid is defined herein as an amount of a SBM in relation to some or all other chemical components within the formation fluid. The concentration of SBM contamination can be a fraction or a percent, such as a weight percentage, a molar percentage, and/or a volume percentage. Furthermore, the concentration of SBM contamination in formation fluid may be (i) a relative amount of some or all components of the SBM within the formation fluid, (ii) a relative amount of one or more olefins of the SBM within the formation fluid, (iii) and/or a relative amount of one or more nuclei of olefins within the formation fluid (e.g., a hydrogen weight percentage of the olefins).
(9)
(10) As seen in
(11) As previously suggested, it is possible to take an integral of the signal under a peak representing a compound in order to determine the amount of any particular compound in the sample. The chemical shift boundaries for integration limits for aromatic, aliphatic, and olefin compounds may be set based on the peaks, or more generally as desired. For example, chemical shift boundaries are shown in Table 1.
(12) TABLE-US-00001 TABLE 1 Chemical shifts and integration limits for aromatic and aliphatic protons: Proton NMR Regions Begin (ppm) End (ppm) TMS 0 0 CH.sub.3 0.5 1.0 CH.sub.2 - Long Chain 1.0 1.4 CH/CH.sub.2 Isoparaffins and 1.4 2.0 Napthenes Alpha-H All Types 2.0 3.0 Hetero - H (O + S) and Ph- 3.0 4.5 CH.sub.2-Ph Olefin H 4.5 6.0 Mono-Aromatic H 6.0 7.2 Di-Aromatic H 7.2 7.8 PNA2 - Di + Tri Aromatic 7.8 8.2 H PNA1 - Tri + Tetra + 8.2 9.3 Aromatic H CHC.sub.13 Solvent 7.24 7.24
(13) In Table 1, the aliphatic group is broken into five subgroups: CH.sub.3 between 0.5 and 1.0 ppm, CH.sub.2-long chain between 1.0 and 1.4 ppm, CH/CH.sub.2 isoparaffins and napthenes between 1.4 and 2.0 ppm, alpha-H between 2 and 3 ppm, and hetero-H between 3 and 4.5 ppm. Also, in Table 1 the olefin group is lumped together between 4.5 and 6.0 ppm. Further, the aromatic group is broken into four subgroups; Mono-Aromatic H between 6 and 7.2 ppm, Di-Aromatic H between 7.2 and 7.8 ppm, PNA2 (also called HeteroAromatic-H between 7.8 and 8.2 ppm, and PNA1 (also called TriAromatic-H) between 8.2 and 9.3 ppm. The tetramethylsilane (TMS) standard is the large signal set by definition at 0 ppm, and CHC.sub.13 solvent is the large signal at 7.24 ppm.
(14) Turning now to
(15) The NMR spectra of
(16) TABLE-US-00002 TABLE 2 .sup.1H NMR results for High SBM (12.3%) and Low SBM (2.3%) samples: Sample Name High Low Total Aliphatic-H 95.6 95.2 Total Olefinic-H 0.6 0.1 Total Aromatic-H 3.8 4.7 HeteroAromatic-H 0.1 0.2 TriAromatic-H 0.3 0.5 DiAromatic-H 1.2 1.5 MonoAromatic-H 2.2 2.5 Alpha-H 7.5 9.2 CH.sub.2 Alpha to 2 0.3 0.4 Aromatics Alpha CH.sub.2 4.9 6.3 Alpha CH.sub.3 2.3 2.5 Beta-H 62.3 61.2 Beta CH.sub.2 13.6 14.2 Paraffinic CH.sub.2 48.6 47 Gamma-H 25.9 24.7
(17) In Table 2, the first three rows are respectively the hydrogen weight percentage totals of aliphatic, olefinic and aromatic compounds contained in the two different SBMs and total to 100%. The next four rows of Table 2 show a breakdown of the aromatic total into four distinct subgroups: heretero-, tri-, di- and mono-aromatics, with their totals equaling the total aromatic listed in the third row. The eighth row (alpha) is an aliphatic, and is broken down in the following three rows into three components (CH.sub.2 alpha to 2 aromatics, alpha CH.sub.2 and alpha CH.sub.3). Similarly, the twelfth row (beta) is an aliphatic that is broken down in the following two rows into two components (beta CH.sub.2 and paraffinic CH.sub.2). The last row (gamma) is an aliphatic, and the gamma, beta and alpha aliphatics substantially total to the total aliphatic shown in the first row.
(18) Particularly notable in comparing the “high” SBM column and “low” SBM column of Table 2 is that the total olefinic-H weight percentage (0.6%) in the sample with a high level of SBM contamination is substantially six times the total olefinic-H weight percentage (0.1%) in the sample with a low level of SBM contamination which correlates well with the gas chromatography determination that the high SBM sample contained 12.3% SBM, and the low SBM sample contained 2.3% SBM (a factor of 5.3). In addition, it is noted that the olefinic content of the SBM is approximately 5%-6%, with the remainder being aliphatic. Thus, where the sample contained approximately 12.3% SBM, it would be expected that the olefins would constitute approximately 0.6% of the sample (12.3%×0.05=0.615%) as was measured, and where the sample contained approximately 2.3%, it would be expected that the olefins would constitute approximately 0.1% of the sample (2.3%×0.05=0.115%).
(19) In one embodiment, the hydrogen weight percentage of the olefins in a formation fluid is measured by integrating the area under the spectral olefinic NMR peaks and dividing that by the area under the NMR peaks of the spectrum (e.g., all of the NMR peaks of the spectrum). In another embodiment, the hydrogen weight percentage of the olefins in a formation fluid is measured by integrating the area under the spectral curve corresponding to a chemical shift of between 4.5 and 6 ppm and dividing that by the area under the entire spectral curve for hydrocarbons (e.g., 0.5 ppm to 9.3 ppm). According to another embodiment useful for most oil samples, but in particular for heavy oil samples, a known amount of a standard, such as tetramethylsilane (TMS) is added to the sample. After a spectral NMR experiment, the area under the olefin peaks or olefinic area (6.0 ppm to 4.5 ppm) is compared to the area under the TMS peak (at 0 ppm) in order to derive the hydrogen weight percentage of olefins in the sample. The total weight percentage of olefins may then be derived by knowing the hydrogen weight fraction of TMS and the hydrogen weight fraction of the SBM. It is noted that a standard other than or in addition to TMS may be utilized.
(20) In one aspect, the weight percentage of the olefins may be converted to a weight percentage of the sample that is SBM by knowing the constituents of the SBM. Thus, by way of example only, if the olefins in the SBM are 5% by weight of the SMB, and olefins are 1.0% by weight of the sample, then the SBM is 20% by weight of the sample. Similarly, if the olefins in the SBM are 6% by weight of the SBM, and olefins are 0.2% by weight of the sample, then the SBM is 3% by weight of the sample.
(21) It is noted with respect to the NMR measurements, that NMR measures the percentage of hydrogen (also called hydrogen weight percentage) attributable to the different groups. A weight percentage of a compound can then be inferred based on a knowledge of the hydrogen content of the SBM and of the oil, and of the standard, if one is used.
(22) In one embodiment, a formation fluid (e.g., oil sample) obtained from a formation is obtained by a sample obtaining tool located in a wellbore (e.g., a wireline tool). The sample is brought uphole and subjected to an NMR spectral experiment (test). The concentration of contamination of the sample by SBM is then found by determining the olefinic content of the sample via the NMR spectral test and through knowledge or an estimate of olefinic weight percentage in the SBM.
(23) In another embodiment, a formation fluid (e.g., oil sample) obtained from a formation is obtained by a sample obtaining tool located in a wellbore (e.g., a wireline tool). The sample is brought uphole, and TMS and/or another standard is added to the sample which is then subjected to an NMR spectral experiment (test). The concentration of contamination of the sample by SBM is then found by comparing the olefinic content of the sample via the NMR spectral test to the standard content and using that comparison as well as knowledge or an estimate of olefinic weight percentage in the SBM.
(24) According to one aspect, an indication of the olefinic content of the formation fluid is used to estimate the concentration of SBM contamination of the sample. In one embodiment, the indication of the olefinic content is obtained by subjecting the sample to an NMR spectral test and inspecting the peaks in the 4.5 to 6.0 ppm portion of the spectrum. In another embodiment, the indication of the olefinic content is obtained by subjecting the sample to an NMR spectral test and inspecting the “olefin alpha” peak at approximately 1.9 to 2.1 ppm. While the olefin alpha peak is an aliphatic peak, it represents the amount of a particular aliphatic compound that is adjacent an olefin, thereby indicating the presence of an olefin. If a correlation is known for the area under this peak with the expected area under the olefinic peaks, then this peak can be used in lieu of the olefinic peaks in determining the olefinic content and hence the contamination. In one aspect, a correlation may be found by investigating numerous samples with different olefinic contents and comparing the area under the olefin alpha peak with the area under one or more of the olefinic peaks. In another embodiment, a correlation is found by comparing the area under the olefin alpha peak to the known olefin content of an SBM. The correlation can also be determined from the composition of the SBM.
(25) The methods previously described may be conducted with NMR spectral equipment located uphole or downhole.
(26) In another embodiment, rather than utilizing a .sup.1H proton NMR spectrum of a formation fluid (e.g., oil sample) in assessing whether or to what extent a formation fluid is contaminated with a SBM, a .sup.13C NMR spectrum (carbon chemical shift) is obtained utilizing equipment located uphole or downhole and used to assess whether or to what extent a formation fluid is contaminated with a SBM. According to one aspect, by running a set of experiments on a number of different hydrocarbons, it can be determined that .sup.13C chemical shifts are largely correlated to .sup.1H proton chemical shifts. A correlation is shown in Table 3.
(27) TABLE-US-00003 TABLE 3 Chemical shifts and integration limits for attached carbon atoms: .sup.13C Attached carbon chemical .sup.1H chemical atom shift (ppm) shift (ppm) Terminal, single- 14-17 0.9 bonded (e.g., CH.sub.3) Adjacent to terminal, 22-23 single-bonded Internal, single- 29-33 1.3 bonded (e.g., CH.sub.2) Internal, adjacent to 34-40 2 double-bonded (e.g., olefin-alpha) Adjacent to aromatic 21-38 2.0-2.3 Terminal, double 114-115 4.9-5.1 bonded (olefin) Internal, double 125-140 5.5-5.8 bonded (olefin) Aromatic 125-130 6.0-8.2
(28) From Table 3, it can be seen that the presence of a .sup.13C chemical shift signal at between substantially 114 and 115 ppm is indicative of the presence of a terminal double-bonded olefin that may be found in certain SBMs and is rarely found in crude oil. In addition, the presence of a chemical shift signal at between substantially 125 and 140 ppm may be indicative of the presence of an internal double-bonded olefin that may be found in an SBM and is rarely found in crude oil. However, because the .sup.13C chemical shift of aromatics is at substantially 125-130 ppm, if there are aromatics in the sample, the presence of the aromatics can complicate a determination as to whether a signal relates to a terminal double-bonded olefin or not. Thus, in one embodiment, a chemical shift signal at between substantially 131 and 140 ppm is used to identify internal double-bonded olefins present in the sample.
(29) An example of an oil containing olefins that can be used in an SBM is squalene (C.sub.30H.sub.50) which is a natural hydrocarbon obtained from vegetable and shark liver oils. Squalene contains as many as six internal double bonds per molecule. As seen in
(30) In another embodiment, where information as to the aromatic content (or lack thereof) in the crude oil is independently available, a chemical shift signal, between substantially 125 and 140 ppm, is used to identify the presence of an SBM.
(31) In one embodiment, the double-bonded carbon atom weight fraction (hereinafter referred to as the olefinic content) in a formation fluid (e.g., oil sample) is measured by integrating the area under the .sup.13C spectral olefinic NMR peaks and dividing that by the area under the .sup.13C NMR peaks of the spectrum (e.g., all of the .sup.13C NMR peaks of the spectrum). In another embodiment, the olefinic content in a formation fluid is measured by integrating the area under the spectral curve corresponding to a chemical shift of between about 110 and 150 ppm, or the areas under the spectral curve corresponding to a chemical shift of between about 110 and 120 ppm and 130 and 140 ppm and dividing that by the area under the entire spectral curve for hydrocarbons (e.g., 14 ppm to 150 ppm). As with the proton spectroscopy, if desired, a standard may be added to the sample, and after a .sup.13C spectral NMR experiment, the area under the olefin peaks or olefinic area is compared to the area under the peak of the standard in order to derive the weight percentage of olefins in the sample.
(32) In one aspect, as with the proton spectroscopy, the olefinic content determined via a .sup.13C spectral NMR experiment may be converted to a weight percentage of the sample that is SBM by knowing the constituents of the SBM.
(33) In one embodiment, a formation fluid (e.g., oil sample) obtained from a formation is obtained by a sample obtaining tool located in a wellbore (e.g., a wireline tool). The sample is brought uphole and subjected to a .sup.13C NMR spectral experiment (test). The concentration of contamination of the sample by SBM is then found by determining the olefinic content of the sample via the .sup.13C NMR spectral test and through knowledge or an estimate of olefinic weight percentage in the SBM.
(34) The methods previously described may be conducted with .sup.13C NMR spectral equipment located uphole or downhole.
(35) In another embodiment, a formation fluid (e.g., oil sample) obtained from a formation is obtained by a sample obtaining tool located in a wellbore (e.g., a wireline tool). The sample is brought uphole, and a standard is added to the sample which is then subjected to a .sup.13C NMR spectral experiment (test). The amount of contamination of the sample by SBM is then found by comparing the olefinic content of the sample via the NMR spectral test to the standard content and using that comparison as well as knowledge or an estimate of olefinic weight percentage in the SBM.
(36) According to one aspect, an indication of the olefinic content of the formation fluid found as a result of a .sup.13C NMR spectral test is used to estimate the amount of contamination of the sample by SBM. In one embodiment, the indication of the olefinic content is obtained by subjecting the sample to a .sup.13C NMR spectral test and inspecting the peaks in the 110-150 ppm (or 110-120 ppm and 130-140 ppm) portion of the spectrum. In another embodiment, the indication of the olefinic content is obtained by subjecting the sample to an NMR spectral test and inspecting the “internal, adjacent to double-bonded” peak at approximately 34 to 40 ppm. While the “internal, adjacent to double-bonded” peak is not an olefinic peak, it represents the amount of a particular compound that is adjacent an olefin, thereby indicating the presence of an olefin. If a correlation is known for the area under this peak with the expected area under the olefinic peaks, then this peak can be used in lieu of the olefinic peaks in determining the olefinic content and hence the contamination. In one aspect, a correlation may be found by investigating numerous samples with different olefinic contents and comparing the area under the olefin alpha peak with the area under one or more of the olefinic peaks. In another embodiment, a correlation is found by comparing the area under the olefin alpha peak to the known olefin content of an SBM.
(37) In another embodiment, because the .sup.13C chemical shift of “adjacent to aromatic” is at substantially 21 to 38 ppm, if there are aromatics in the sample, the presence of the aromatics can complicate a determination as to whether a signal relates to an adjacent to double-bonded olefin. Thus, in one embodiment, a chemical shift signal at between substantially 39 and 40 ppm is used to identify “adjacent to double-bonded” olefins present in the sample. In another embodiment, where information as to the “adjacent to aromatic” and/or aromatic content (or lack thereof) in the crude oil is independently available, a chemical shift signal between substantially 34 and 40 ppm, is used to identify the presence of an SBM.
(38) In one embodiment, chemical shift information from both the proton NMR spectrum and the .sup.13C spectrum may be used together to determine the presence and/or extent of an olefin in a formation fluid. This may be done by looking at different parts of the spectra in order to make determinations and/or in order to confirm determinations.
(39) Turning to
(40) The wireline tool 100 also includes a NMR module 112 for analyzing at least a portion of the fluid in the flow line 108 (e.g., an oil sample). In illustrative embodiments, the NMR module 112 applies a homogeneous static magnetic field to the fluid in the flow line 108 and generates a spectral pulse sequence (e.g., a ninety degree or one hundred eighty degree pulse followed by an acquisition period). In this manner, the NMR module 112 performs a spectral NMR analysis of the fluid within the flow line 108 to obtain a chemical shift spectrum. Further details regarding downhole NMR systems that can perform NMR spectroscopy in a flow line can be found in U.S. Pat. No. 8,471,559, issued on Jun. 25, 2013, and U.S. Patent Application Publication No. 2012/0169334, published on Jul. 5, 2012. Each of these references is incorporated by reference herein in their entireties.
(41) The wireline tool 100 may contain a processor or processors for generating a spectrum from the detected signals and analyzing the spectrum, as described herein. Alternatively or in addition, a processor or processors 114 may be located uphole, and signals may be sent from the wireline tool 100 uphole for processing. The processor may be a programmed computer, a dedicated processor, a system of microprocessors or other circuitry capable of analyzing the NMR data obtained by the NMR module 112 in order to determine the concentration of contamination of the sample.
(42) After the NMR module 112, the formation fluid (e.g., the oil sample) may be pumped out of the flow line 108 and into the wellbore 102 through a port 118. Some of the formation fluid may also be passed to a fluid collection module 116 that includes chambers for collecting fluid samples and retaining samples of the formation fluid for subsequent transport and testing at the surface (e.g., at a testing facility or laboratory).
(43) In illustrative embodiments, the concentration of contamination determined by the NMR module 112 and processor 114 may be reported to an operator or may be used to automatically control whether a fluid sample is kept for storage in the fluid collection module 116 or jettisoned into the wellbore 102 through the port 118. In this manner, samples obtained by the wireline tool 100 may be monitored for contamination and, when a sample containing an “acceptable” concentration of contamination is obtained, the sample may be stored in the fluid collection module 116 and brought uphole for further analysis. The acceptable concentration may be determined relative to a threshold value.
(44) The methods described herein can be implemented by various other wellbore tools and wellbore tool configurations. For example, the methods described herein can be implemented by a wellbore tool that is conveyed by other means, such coiled tubing. Furthermore, the methods described herein can also be applied in logging-while-drilling (LWD) operations, sampling-while-drilling operations, measuring-while-drilling operations, or any other operation where monitoring of formation fluid is performed.
(45) Furthermore, in some embodiments, the methods described herein are performed in a wellbore using a wellbore tool. In other embodiments, the methods described herein are performed at the surface using a laboratory NMR system on formation fluid that has been brought to the surface. Also, the the methods described herein can be used to analyze a variety of different types of formation fluids. In particular, the methods can be used to analyze light oils, heavy oils, biodegraded oils, water washed oils, live oils, dead oils, gases, and water.
(46) There have been described and illustrated herein several embodiments of methods of determining mud contamination of a formation fluid. While particular embodiments and aspects have been described, it is not intended that the disclosure be limited thereto, and it is intended that the claims be as broad in scope as the art will allow and that the specification be read likewise. Thus, while particular ppm ranges have been set forth for olefins and other groups or subgroups, it will be appreciated that the ranges are relative to a standard. In addition it will be appreciated that other ranges could be specified. In addition, it will be appreciated that while multiple olefins are described as being identified, the methods and apparatus may be used to identify a single olefin in an SBM, and if the amount of that olefin is known relative to the SBM itself, the extent of contamination of the formation fluid can be determined. Also, while identification of olefins was described utilizing a proton spectrum and/or a .sup.13C spectrum, it will be appreciated that other NMR chemical shift spectra could be utilized. It will therefore be appreciated by those skilled in the art that yet other modifications could be made. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims. In the claims, means-plus-function clauses, if any, are intended to cover the structures described herein as performing the recited function and not only structural equivalents, but also equivalent structures. It is the express intention of the applicant not to invoke 35 U.S.C. §112, paragraph 6 for any limitations of any of the claims herein, except for those in which the claim expressly uses the words ‘means for’ together with an associated function.