Abstract:
A method for analytically separating properties of hydrocarbon materials from other materials in a downhole environment, the method including: performing nuclear magnetic resonance (NMR) measurements downhole; determining a signal for sodium-23 ( 23 Na) from the NMR measurements; and associating the  23 Na signal with the other materials. A computer program product, an apparatus and additional methods are provided.

Description:
CROSS REFERENCE TO RELATED APPLICATION 
     The present application is filed under 37 CFR §1.53(b) and 35 U.S.C. §120 and claims priority to U.S. Provisional Patent Application Ser. No. 60/951,293, filed Jul. 23, 2007, the entire contents of which are specifically incorporated herein by reference in their entirety 
    
    
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The invention disclosed herein relates to geophysical assessments using nuclear magnetic resonance techniques and, in particular, to techniques for discerning water from hydrocarbon fluids. 
     2. Description of the Related Art 
     Many petroleum reservoirs around the world contain salty formation water. Formation water can be of meteoric or connate origin, or from a mixture of both. Although seawater contains salt of about 30 kppm, the average petroleum reservoir having connate brine contains about 80 kppm of salt. Many petroleum reservoirs that are saturated with salt, such as those common to the major oil-producing or gas-producing fields in the Middle East, contain salt as high as 250 kppm, (i.e., the salt may represent up to about 25% of the weight of the brine). Connate brine contains mainly NaCl salt. 
     Current NMR wireline and logging techniques only use measurements for protons for a good reason. The proton has a natural abundance of nearly 100%. In addition, the proton has the strongest per-sample signal intensity, as determined by f 0   3 I(I+1), where f 0  is the NMR frequency and I is the spin quantum number. Because both the hydrocarbon phase and water (brine) phase contain protons, properties of each phase can not be determined from the proton signal intensity alone. Accordingly, the capability of traditional proton NMR techniques for discerning hydrocarbon from salty water downhole has its limitations. 
     Further, since brine is a conductive liquid, its presence in the formation has a negative effect on the signal quality of many other logging instruments, considering those instruments that are based on the transmitting and receiving of electrical power. Such instruments may include, but are not limited to, nuclear magnetic resonance (NMR) logging instruments and galvanic and inductive logging devices. Poor signal to noise ratio in a salty environment makes it even more difficult to discern hydrocarbon from water. 
     The current arts of NMR logging techniques discern hydrocarbon from brine based on their contrast in relaxation times (i.e., the longitudinal relaxation time T 1  and the transverse relaxation time T 2 ) and the fluid diffusivities, D. Although these techniques have been used successfully downhole, the applicability of these approaches relies heavily on the robustness of these contrasts and the adequate signal-to-noise ratio (SNR). For light hydrocarbons such as volatile and very low-viscosity oils, the water and oil diffusivity contrast is very small; it would be very difficult to separate oil and water from NMR responses, especially in the rocks with large pores and in vuggy carbonates. 
     On the other hand, determination of formation water resistivity is an important step for induction or resistivity-based saturation estimates. Although in many mature reservoirs the Rw value is well known, for exploration wells, it is important to be able to determine formation resistivity or the equivalent of formation water salinity. 
     The poor signal-to-noise ratio (SNR) and the possibility of mixing  23 Na signals from borehole with signals from protons (i.e., hydrogen) in formation fluids have been the main reason for not considering  23 Na NMR logging measurements using the current NMR logging instrument configurations. 
     Therefore, what are needed are techniques for discerning a presence of hydrocarbon materials from salty water downhole. Preferably, the techniques may be implemented using existing technologies, such as instruments using nuclear magnetic resonance (NMR). 
     BRIEF SUMMARY OF THE INVENTION 
     Disclosed is a method for analytically separating properties of hydrocarbon materials from other materials in a downhole environment, the method including: performing nuclear magnetic resonance (NMR) measurements downhole; determining a signal for sodium-23 ( 23 Na) from the NMR measurements; and associating the  23 Na signal with the other materials. 
     Also disclosed is a computer program product including machine readable instructions stored on machine readable media, the instructions for analytically separating properties of hydrocarbon materials from other materials in a downhole environment, by implementing a method including: performing nuclear magnetic resonance (NMR) measurements downhole; determining a signal for sodium-23 ( 23 Na) from the NMR measurements; and associating the  23 Na signal with the other materials. 
     Further disclosed is an apparatus for performing nuclear magnetic resonance (NMR) measurements in a wellbore, the apparatus including: a magnet configuration adapted for separating a proton response from a sodium-23 ( 23 Na) response for the NMR measurements. 
     Also provided is a method for analytically separating properties of hydrocarbon materials from other materials in a downhole environment, the method including: performing a first nuclear magnetic resonance (NMR) measurement for sodium-23 ( 23 Na) at a resonance frequency within a window of homogeneous magnetic field; performing a second nuclear magnetic resonance (NMR) measurement for hydrogen ( 1 H) at another resonance frequency within a window of homogeneous magnetic field; determining a signal for the  23 Na from the first NMR measurement; determining another signal for the  1 H and the  23 Na from the second NMR measurement; and separating the signal and the another signal to determine the properties of the hydrocarbon materials from the other materials. 
     Another embodiment of the invention includes a method for determining formation salinity variation when the oil and brine proton NMR response can be discerned from proton NMR measurements, the method including: performing proton and sodium nuclear magnetic resonance (NMR) measurements within a wellbore penetrating the formation; determining oil-filled and brine-filled porosity volumes separately with proton NMR parameters including at least one of a relaxation time, and a diffusivity, determining a magnitude of a sodium-23 ( 23 Na) NMR signal which represents brine, where the  23 Na NMR signal amplitude is pre-calibrated against a known salinity brine source; determining the salinity of brine from a ratio of magnitude of  23 Na signal and the brine filled porosity volume; where a variation of salinity as a function of measured depth along the bore hole is an indicator of at least one of mud filtrate invasion change and variation in native formation water salinity. 
     In addition, a method for determining water saturation in a formation is provided and includes: performing nuclear magnetic resonance (NMR) measurements within a wellbore penetrating the formation; determining a signal for sodium-23 ( 23 Na) from the NMR measurements; and using a known salinity for the water, determining water saturation in the wellbore from the signal. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The subject matter which is regarded as the invention is particularly pointed out and distinctly claimed in the claims at the conclusion of the specification. The foregoing and other features and advantages of the invention are apparent from the following detailed description taken in conjunction with the accompanying drawings in which: 
         FIG. 1  depicts aspects of well logging with an nuclear magnetic resonance (NMR) apparatus; 
         FIG. 2A  and  FIG. 2B , collectively referred to herein as  FIG. 2 , depict sensitive volumes in a gradient magnetic field; 
         FIG. 3  depicts a shift of sensitive volume location along the radial direction from the NMR tool, under a given operation frequency excitation; 
         FIG. 4A  and  FIG. 4B , collectively referred to as  FIG. 4 , depicts relative sensitive volumes location of sodium and proton at a same resonance frequency and the shift of the sensitive volumes as the result of the frequency being shifted slightly.  FIG. 4A  depicts the responses to a traditional gradient NMR logging instrument.  FIG. 4B  depicts exemplary responses to a barrel shaped magnet. 
         FIG. 5  depicts an embodiment of a magnet suited for practicing the teachings herein; and 
         FIG. 6  depicts radius r, in relation to frequency. 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The teachings herein take advantage of various unique nuclear magnetic resonance (NMR) properties of sodium-23 ( 23 Na) to provide for separate determination of properties of water and hydrocarbon fluids when the water and hydrocarbon fluids reside downhole. 
     For perspective, this disclosure provides a review of techniques for well logging using nuclear magnetic resonance (NMR) technology; some background on NMR measurements and analyses; and, embodiments for using a  23 Na signal for separation of water and hydrocarbon fluids. 
     As discussed herein, the term “separation” generally refers to analytical separation of properties associated with water, brine and other such fluids from the properties of hydrocarbons downhole. Separation is generally not meant to imply refining of mixtures of water, brine and hydrocarbon fluids such that physical separation is achieved. Rather, the term “separation” generally implies successful determination of properties, such that a user of the technology determines some benefit has been achieved. Prior to considering aspects of the teachings herein, aspects of geophysical exploration using nuclear magnetic resonance (NMR) technology is provided. The terms “water,” “brine,” and other such terms are generally related to fluids and other materials that are found downhole and that do not include hydrocarbon materials, or at least appreciable quantities of hydrocarbon materials. The term “proton” generally makes reference to protons bound in hydrogen, whether included in water or hydrocarbon materials. 
     Turning to  FIG. 1 , consider aspects of downhole NMR characterizations, using a non-limiting embodiment of a wireline logging device. One skilled in the art will recognize that the techniques disclosed herein can be applied with other embodiments, such as logging-while-drilling (LWD) or measurements-while-drilling (MWD) operations. 
       FIG. 1  shows a well logging apparatus disposed in a wellbore  22  penetrating earth formations  23 ,  24 ,  26 ,  28  for making measurements of properties of the earth formations  23 ,  24 ,  26 ,  28  downhole. The wellbore  22  in  FIG. 1  is typically filled with a fluid  34  known in the art as “drilling mud.” A “sensitive volume,” shown generally at  58  and whose shape may vary due to different magnet designs, is disposed in one of the earth formations, shown at  26 . The sensitive volume  58  is a predetermined portion of the earth formations  26  in which nuclear magnetic resonance (NMR) measurements are made, as will be further explained. 
     In typical embodiments, the sensitive volume  58  includes materials such as would be found downhole (below the surface and within or around the wellbore  22 ) including a mixture of fluids including gas, water, drilling fluid, oil and formation fluids that are indigenous to the formations  23 ,  24 ,  26 ,  28 . 
     A string of logging tools  32 , which can include an NMR apparatus according to the present invention, is typically lowered into the wellbore  22  by, for example, an armored electrical cable  30 . The cable  30  can be spooled and unspooled from a winch or drum  48 . The tool string  32  can be electrically connected to surface equipment  54  by an insulated electrical conductor (not shown separately in  FIG. 1 ) forming part of the cable  30 . The surface equipment  54  can include one part of a telemetry system  38  for communicating control signals and data to the tool string  32  and computer  40 . The computer may also include a data recorder  52  for recording measurements made by the apparatus and transmitted to the surface equipment  54 . Typically, the computer includes a variety of input/output devices and other supporting devices to enhance the operation of the apparatus and estimations performed by use thereof. An NMR probe  42  can be included in the tool string  32 . 
     Circuitry for operating the NMR probe  42  can be located within an NMR electronics cartridge  44 . The circuitry can be connected to the NMR probe  42  through a connector  50 . The NMR probe  42  is typically located within a protective housing  43  which is designed to exclude the drilling mud  34  from the interior of the probe  42 . The function of the probe  42  will be further explained. 
     Other well logging sensors (not shown separately for clarity of the illustration in  FIG. 1 ) may form part of the tool string  32 . As shown in  FIG. 1 , one additional logging sensor  47  may be located above the NMR electronics cartridge  44 . Other logging sensors, such as shown at  41  and  46  may be located within or below the bottom centralizer  57 . The other sensors  41 ,  46 ,  47  can be of types familiar to those skilled in the art. 
     Other aspects of the exemplary embodiment of the NMR probe  42  are provided in U.S. Pat. No. 5,712,566, entitled “Nuclear Magnetic Resonance Apparatus and Method,” issued Jan. 27, 1998 to Taicher et al., and incorporated herein by reference in it&#39;s entirety. Another non-limiting example is disclosed in U.S. Pat. No. 4,710,713, also issued to Taicher et al, and also incorporated by reference herein in it&#39;s entirety. It should be recognized that these embodiments of NMR tools are exemplary only, and not limiting of the teachings herein. A commercially available and exemplary embodiment of an NMR instrument is the MREX™, available from Baker Hughes, Incorporated of Houston Tex. 
     One skilled in the art will recognize that while the teachings herein may be performed downhole, they are also applicable to evaluations conducted on the surface, such as in a laboratory. Further, and as discussed elsewhere herein, at least a portion of an evaluation or determination may be performed in one place or another. For example, a property of a constituent may be determined in a laboratory, while other measurements and determinations are performed downhole. 
     As a matter of convention, one should note that the variables used herein appear throughout the disclosure. Accordingly, previously defined variables are generally not reintroduced. For convenience of referencing, the following representations are some of the definitions applied herein, or related to the teachings herein: B 0  represents static field strength for a magnetic field; B 1  represents radiofrequency (RF) field strength; D represents diffusivity; f represents a proton fraction; G represents RF field gradient strength; R represents a resistivity; r represents a radius from a center of the wellbore; M represents echo magnetization amplitude; where M z (t) represents a longitudinal magnetization, which involves a time constant T 1 , where T 1  is the time required for the magnetization vector to be restored to 63% of its original amplitude (referred to as “longitudinal relaxation time”); M xy  represents a transverse magnetization, which involves a time constant T 2 , where T 2  is the time required for the magnetization vector to drop to 37% of its original amplitude (referred to as “transverse relaxation time”); and T w  represents a relaxation wait time. 
     A variety of techniques are provided herein for using an NMR signal associated with sodium-23 ( 23 Na) to provide for analytical separation of hydrocarbon materials from non-hydrocarbon materials downhole. 
     A first technique involves taking advantage of the relaxation time for  23 Na. At a given field strength, the nominal  23 Na NMR signal intensity is 0.0925 that of the proton. For very conductive samples, such as that of salt-saturated reservoirs, the relative sensitivity of  23 Na, computed from f 0   2 I(I+1), is about 0.35. Thus, it is favorable to apply the sodium NMR measurements in those salty wells. First, the signal for  23 Na is strong. Secondly, the relative sensitivity to  23 Na in comparison to protons is better than that in resistive media. Compared to proton relaxation times,  23 Na NMR for NaCl solution is a few orders of magnitude shorter, (e.g., in a range of about 10 milliseconds compared to a range in seconds for protons). Therefore, the magnetization time for  23 Na may be considered “substantially shorter” than the magnetization polarization time for the protons. Therefore, in a given amount of time, a substantial number of repetitive experiments can be performed to improve the SNR of  23 Na measurements. This provides a basis for at least statistically overcoming the small signal intensity associated with  23 Na. The capability of conducting quick and repetitive measurements can result in up to a ten fold of SNR improvement for sodium NMR for a single frequency measurement. Advantageously, because of the short relaxation time of  23 Na, it is not important to have a long pre-polarization magnet. 
     Another technique for using the NMR signal associated with  23 Na calls for using a magnet configuration that provides a large sensitive volume. Since the inception of NMR logging, concerns were raised of possible interference of  23 Na signal from salt-saturated borehole mud fluid to interfere with proton NMR signal from the formation fluid. For gradient field NMR instruments such as MREX™, the signal associated with  23 Na and obtained in the borehole has been proven too weak to be of use. The tiny sensitive volume, unfavorable tip angles, and the small relative intensity of  23 Na, have all contributed to the absence of a  23 Na signal in the proton NMR data. 
     However, for a different configuration of magnet, such as a barrel magnet or a combination of barrel and bar magnet  400  (reference may be had to  FIG. 5 ), a substantially large window of relatively homogeneous magnetic field, often called the “sweet spot,” can be achieved. Thus, it is possible to select the  23 Na resonance frequency such that the NMR sensitive volume falls into the sweet spot. The large sensitive volume increases the NMR signal strength, and compensates for the lower relative intensity of the NMR measurement for  23 Na. A difference in the sensitive volume between the gradient magnetic field used in the MREX configuration is illustrated in  FIG. 2A . In  FIG. 2B , a barrel and bar magnet configuration is depicted. The curves provided in  FIG. 2  are useful for depicting aspects of prior art instruments (e.g., MRIL tool by Halliburton Corporation of Houston Tex. and MREX tool by Baker Hughes Inc.) and embodiments of the teachings herein (e.g., use of a barrel-shaped magnet). 
     Exemplary barrel magnets  400  and combinations of barrel and bar magnets  400  are described in U.S. Pat. Nos. 6,489,872 and 6,828,892 by Fukushima and Jackson, respectively. The disclosures of these patents are incorporated herein by reference in their entirety. Other configurations for magnets may be used. As an example, magnet configurations provided in the MAGTRAK design of Baker Hughes, Incorporated may be used. 
     Use of a barrel magnet  400  and other similar configurations provides certain advantages. For example, one advantage of the barrel-shaped magnet configuration for  23 Na NMR is that the signal is further away from the borehole, which is a large source of error in measurements for sodium. 
     Using these design principles, the volume of a relatively homogeneous magnetic field strength at the sweet spot is larger than in other traditional designs. Thus, more nuclei are included in the volume resulting in the stronger  23 Na. Comparison may be made to CMR or NMR Mole (Manz et al, Journal of Magn Reson, v. 183 (2006)) designs, the barrel shaped magnet  400  has a stronger magnetic strength at the sweet spot. The improved magnetic strength, coupled with the large sensitive volume, further make the  23 Na measurement practical. 
     In a further technique for using an NMR signal associated with sodium-23 ( 23 Na) to provide for analytical separation of hydrocarbon materials from non-hydrocarbon materials downhole, measurements may be performed where a shift to a resonance frequency that is off of the sweet spot is performed. Shifting of the resonance frequency provides for verification of any  23 Na signals. 
       FIG. 3  depicts a shift of sensitive volume location along the radial direction from the NMR tool, under a given operation frequency excitation. Since  23 Na has a smaller gyromatic ratio than that of protons, the sensitive volume is much closer to the borehole than that of protons. 
     The larger sensitive volume is only one of the advantages of the barrel magnet for  23 Na NMR measurements. At a given resonance frequency, the magnetic field strength for  23 Na to reach resonance condition is about four times that of protons. 
     Generally, in the prior art, the NMR signal associated with  23 Na may overlap with the NMR signal associated with protons for the same excitation, as illustrated in  FIG. 4A , although the signal of the  23 Na may be quite weak. Accordingly, shifting of the NMR frequency generally results in a similar signal for the  23 Na and H, as shown in the dotted line in  FIG. 4A . This is exhibited as signal overlapping. Thus, the  23 Na and H constituents are usually not well distinguished by use of different resonance frequencies. 
     However, using the barrel magnet configuration, if  23 Na resonance frequency is set at the sweet spot, then the corresponding proton sensitive volume will be much deeper and much smaller, as shown in  FIG. 4B . Accordingly, the signal for the proton is made very weak. This provides for resolving the  23 Na signal. Furthermore, if the  23 Na resonance frequency is slightly shifted away from the sweet spot, as shown in the dotted circles in  FIG. 4B , the proton signal intensity corresponding to this second frequency is substantially the same but the  23 Na signal will be substantially smaller than that on the sweet spot. Therefore, even if the proton signal overlaps with the  23 Na signal, the proton component can be easily removed by computing the difference of the two frequency measurements. 
     Further techniques for diminishing the NMR signal associated with protons include use of fast measurement repetition. That is, because the NMR relaxation time of brine associated with  23 Na is approximately 10 ms, one can set very short wait times, T w , (normally three times the longitudinal relaxation time, T 1 ). However, light hydrocarbon has very long proton relaxation time, T 1 . Accordingly, by using short wait times, T w , the proton signal is underpolarized because of its longitudinal relaxation time, T 1 . This results in further reducing unwanted contributions to the  23 Na NMR signal. 
     A technique for separation of brine from hydrocarbon is now provided. In order to separate the hydrocarbon phase from the brine phase, two measurements are taken with NMR logging instruments. Two frequencies corresponding to the  23 Na and  1 H are tuned at the sweet spot of a static magnetic field. The two measurements are separately calibrated. Thus, the  23 Na resonance frequency measurement acquires only the brine phase data, while the proton resonance frequency measurement acquires both the brine and hydrocarbon phase data. If the resonance frequency for  23 Na is f Na , the proton resonance at the same sensitive volume is substantially approximately f H =3.7804·f Na . 
     In many cases, at least one of salinity and resistivity of formation water and mud filtrate is known. For example, knowledge may be obtained from a water sample test or from historical data for a given formation. In such cases, the  23 Na signal strength can be converted to the volumetric quantity of brine when salinity is known. The difference between  1 H-based volumetrics and  23 Na-based volumetrics (porosity) is the hydrocarbon-bearing volume. 
     An application is also provided to determine the formation water resistivity, R w . In the case where the formation water salinity is unknown, the measurement of  23 Na in the water-bearing section can provide for determination of the formation water resistivity, R w . That is, for a water-bearing section, the quantification of  23 Na from Na NMR measurement and the porosity from proton NMR measurement, or other porosity measurement, such as density porosity, yields the reservoir or flushed-zone salinity determination. This quantity may be used for calculation of the formation water resistivity, R w . Together with R t =R o  for water-saturated rock from induction or resistivity log measurement, and the porosity from proton NMR, one determines the cementation factor, m, and the porosity, φ, using the Archie equation, provided as Eq. (1):
 
 S   w =[( a/φ   m )*( R   w   /R   t )] (1/n)   (1);
 
where:
         S w  represents water saturation;   φ represents porosity;   R w  represents formation water resistivity;   R t  represents observed bulk resistivity;   a represents a constant (often taken to be 1);   m represents a cementation factor (varies about 2); and,   n represents a saturation exponent (generally about 2).       

     For water based mud (WBM) filtrate flushed water-saturated zone, the salinity of brine, which is a mixture of filtrate and native reservoir brine, can be calculated from the  23 Na NMR and porosity from proton NMR logs. Comparisons of these results with results of resistivity logging based R xo  may be made for further insight into properties downhole. Some further aspects are now discussed with reference to  FIG. 6 . 
     Refer now to  FIG. 6 , where radius from a center of the wellbore  22 , r, is shown as a function of frequency, f. At the frequency selected for sodium, f Na , the proton signal is very weak and the sensitive volume is deep. At the frequency selected for hydrogen, f H , the sodium  23  signal is small because sensitive volume is small due to large gradient. 
     As shown in  FIG. 4B , the static field strength for the magnetic field, B 0 , decreases rapidly to a plateau, and then again after the plateau (i.e., the “sweet spot”). In combination, it may be realized that slightly shifting the frequency used for sodium-23 causes the sodium signal intensity to decrease significantly, while the proton signal intensity remains approximately the same. This may be used to verify presence of sodium-23. 
     As the relaxation wait time, T w , for sodium is relatively fast, while comparatively slow for the protons, certain advantages are realized. For example, short wait times may provide for a large repetition of measurements and improved reliability. This helps to further eliminate the proton signal and only require short echo trains. Further, there is little or no effect in the data from vibration of instrumentation (such as during drilling), and a simple CPMG sequence is realized. 
     Thus, certain advantages are realized. That is, for example, the teachings herein provide for, among other things, direct fluid typing. This is applicable to salt saturated or known salinity reservoirs, and may be performed using both  1 H and  23 Na measurements. More specifically, porosity may be determined by  1 H NMR, water saturation by  23 Na and then hydrocarbon content estimated by subtraction of the  23 Na volume from the  1 H volume. In addition, salinity variation measurements may be performed. This is particularly applicable to cases where  1 H NMR is adequate for fluid typing. This provides for fluid typing (volumetrics) by use of the  1 H NMR signal, and permits users to estimate quantities of injected (sea water) from connate (salt saturated or nearly saturated). 
     In support of the teachings herein, various analysis components may be used, including at least one of a digital system and an analog system. The system may have components such as a processor, storage media, memory, input, output, communications link (wired, wireless, pulsed mud, optical or other), user interfaces, software programs, signal processors (digital or analog) and other such components (such as resistors, capacitors, inductors and others) to provide for operation and analyses of the apparatus and methods disclosed herein in any of several manners well-appreciated in the art. It is considered that these teachings may be, but need not be, implemented in conjunction with a set of computer executable instructions stored on a computer readable medium, including memory (ROMs, RAMs), optical (CD-ROMs), or magnetic (disks, hard drives), or any other type that when executed causes a computer to implement the method of the present invention. These instructions may provide for equipment operation, control, data collection and analysis and other functions deemed relevant by a system designer, owner, user or other such personnel, in addition to the functions described in this disclosure. 
     Further, various other components may be included and called upon for providing for aspects of the teachings herein. For example, a sample line, sample storage, sample chamber, sample exhaust, pump, piston, power supply (e.g., at least one of a generator, a remote supply and a battery), magnet, electromagnet, transmitter, receiver, transceiver, antenna, controller, electrical unit or electromechanical unit may be included in support of the various aspects discussed herein or in support of other functions beyond this disclosure. 
     One skilled in the art will recognize that the various components or technologies may provide certain necessary or beneficial functionality or features. Accordingly, these functions and features as may be needed in support of the appended claims and variations thereof, are recognized as being inherently included as a part of the teachings herein and a part of the invention disclosed. 
     While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications will be appreciated by those skilled in the art to adapt a particular instrument, situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.