Abstract:
An apparatus for detecting one or more organic compounds in a gem, comprising a probe for irradiating a surface of a gem with near infrared radiation, to generate internal reflections of the near infrared radiation within the gem, wherein the internal reflections are substantially diffuse; a near infrared radiation transmissive conduit for collecting internally reflected near infrared radiation from a surface of the gem, the internally reflected energy comprising components which are diffuse; a spectrometer for analyzing the collected internally reflected diffuse near infrared radiation from the gem, to determine if spectral characteristics indicative of at least one organic compound are present in the gem.

Description:
CROSS REFERENCE TO RELATED APPLICATIONS 
   This application is a continuation of U.S. patent application Ser. No. 09/967,357, filed Sep. 28, 2001, now U.S. Pat. No. 7,105,822 issued on Sep. 12, 2006, expressly incorporated herein by reference, and claims the benefit of U.S. Provisional Patent Application No. 60/236,497, filed Sep. 29, 2000, which is expressly incorporated herein by reference. 

   BACKGROUND OF THE INVENTION 
   1. Field of Invention 
   The present invention relates to gems and, more particularly, to a process for detecting the presence of organic compounds which have been used as enhancement/treatment agents to fill surface reaching fissures, fractures, pores and imperfections in gemstones. 
   The process of the present invention uses Near Infrared (NIR) and Mid Infrared (MIR) radiation, reflected diffuse energy and spectroscopic analysis to detect the presence of organic fillers. 
   2. Art Relating to the Invention 
   Gems are a category of minerals that exhibit a unique set of physical and optical characteristics that are reflected in their color, clarity, hardness, degree of transparency and dispersion. These attributes blend together with related properties to define the beauty, desirability and rarity that define a gemstone&#39;s desirability and market value. In most cases, with the exception of pearls and related organic material, gems are generally cut and polished for ornamental purposes. Natural materials can be replicated in the laboratory by various techniques that are typically referred to as laboratory grown or synthetic products. Because of the extreme geochemical conditions of gem material formation, structural issues at an atomic level and the methods of recovery, many gems contain surface reaching fissures, fracture systems and porosity. The presence of imperfections and blemishes can significantly decrease the value of a gem in the market place. For example, two of the most costly chromium-bearing gems, Ruby and Emerald, typically contain surface reaching fissures and fractures that impact on their value. It is a common practice in the jewelry industry to enhance a gem&#39;s appearance and subsequently its beauty, by filling these imperfections with foreign substances, thereby altering the appearance of the reflecting and visually distracting surface reaching fractures. 
   Organic compounds which are conventionally used to enhance the beauty of gems include oils, waxes, epoxy resins and other natural and synthetic resins. These organics are generally undetectable to the human eye. By selecting fillers or enhancement/treatment agents with optical characteristics similar to that of the gemstone, the effectiveness of the masking agent is increased. For example, a Colombian Emerald with a characteristic refractive index of 1.569-1.577 can effectively be altered by using EPON 828, an epoxy resin that has a similar refractive index of 1.573. This near match can create the illusion of significantly greater value. The improvement in appearance can make the difference between a salable and non-salable item and potentially increase the market value of the end product by thousands of dollars. Although commonly sold without disclosure of these additives, the Federal Trade Commission and other government agencies mandate full disclosure of all enhancement agents that are not permanent and ultimately affect the economic position of a consumer. 
   Infrared spectroscopy has been employed to examine gems in the past. Typically, the gem is placed in front of an infrared radiation source and a detector is positioned behind the gem to capture radiation that is transmitted through or emitted from the gem. The radiation source and the detector being in the same line of sight. Due to the scattering of the radiation, the captured radiation does not always provide an adequate “finger print” of the enhancement/treatment agents identity or indicate the quantity of the organic filler present. 
   Another method suggested for detecting organic compounds in gemstones has been Raman Spectroscopy. The Raman microprobe is a laser based analytical device that has been used to detect organic fissure filling, clarity enhancement agents. Although it offers good spatial resolution, it only analyses specific inclusions or points along a fracture and not the total gem simultaneously. The equipment is expensive and implementation of the technique is labor intensive and tedious. In addition, minerals that fluoresce, like ruby, are not good candidates for Raman analysis. Aggregate materials like turquoise, jade and pearl are equally problematic because of excessive signal scattering. 
   There is a need for a quick, simple means to detect the presence of organic compounds in gemstones. 
   SUMMARY OF THE INVENTION 
   It has now been discovered that diffuse reflectance spectroscopy using infrared radiation can be used to effectively detect organic chemical compounds in gems. Thus, the process of the present invention determines whether an organic chemical compound has been used to fill the fractures, pores, or imperfections in a cut gemstone, rough (uncut) gem materials and porous materials like pearls. 
   Diffuse reflection spectroscopy, also referred to as diffuse reflectance spectroscopy, in accordance with the present invention, illuminates the sample with infrared radiation and collects reflected internal energy, optimizing the reflected diffuse internal energy, while minimizing the impact of specular reflected energy. Preferably, the radiation is diffuse. A transparent or translucent solid such as a gemstone reflects energy in several ways. Specular reflection energy is from radiation which is reflected directly off the surface of the sample. Reflected diffuse internal energy is from radiation that has penetrated the sample and has been reflected from within. 
   The process of the present invention analyzes the gem without damaging the gem and in a very short period of time, typically, less than one minute per sample. Conventional analysis for organic fillers as practiced in many gemological laboratories can require as much as two hours per sample, using current analytical techniques. 
   Applicant has found that near infrared (NIR) and mid infrared (MIR) range of radiation provides the best results for analyzing the presence of organics in a gem using diffuse reflectance spectroscopy. Unlike conventional infrared analysis, gemstone samples cannot be manipulated or destructively altered to accommodate the sample holding device. Typically, analytical labs prepare samples to accommodate the sample chamber. Fixed dimension liquid cells, or thin sections are commonly employed to analyze materials. Gems represent a non-standard analytical challenge. Each gem is typically cut for maximum weight and/or yield from a piece of uncut gem material (rough). The high cost of material commonly in the $5,000 to $25,000/ct range (5 carats=1 gram) for cut, high quality gem material dictates the configuration and shape variables of the final product. Since effective, non-destructive testing is essential, the sample presentation methods must present sufficient variability to accumulate the wide range of cutting formats or geometries of gemstones. Several illumination and analytical options based on diffuse reflectance spectroscopy is required to extend the measurement capabilities and range of organic filler detection. 
   The amount of organics in a carrier (gem material) can also affect the choice of diffused reflectance spectroscopy employed in the sampling process. Small amounts of filler or quantification of filler may necessitate an analysis of all light entering the gem by using a total internal reflection cell or its equivalent. 
   Also, the lighter in color the gem, the less radiation that is needed. A darker colored gem will need more radiation or illumination. Also, external or ambient light is preferably minimized or excluded during the process of the present invention. 
   The electromagnetic spectrum is arbitrarily divided in different bands or wavelength regions. One of these spectrum bands is the infrared spectrum band. The infrared spectrum band lies between the red end of visible light at approximately 0.75 μm and extends to the 1,000 μm region. It has been found that near infrared (NIR) and the mid infrared (MIR) region are the most useful for the identification of organic enhancement or alteration agents in various inorganic hosts. As is known, different chemical bonds absorb radiation differently and exhibit unique vibrational patterns based on the energy absorbed. These molecular vibrational patterns can be detected, analyzed and quantified against known standards to determine the presence and amount of different chemical compounds. Also, as is known the sensitivity of this analysis can be greatly improved by the use of Fourier transformation. Additionally, by cooling the sample, the spectrum can be sharpened. 
   In using diffuse reflectance spectroscopy to detect the presence of organic chemical compounds in gems, applicant has found that Fourier transformation can be effectively employed to analyze the detected energy. Fourier transformation is a conventional means to manipulate data and is used in the present invention in a conventional manner. 
   Fourier transformation has been applied to diffuse reflectance spectroscopy which employs infrared radiation and such a process is called diffuse reflectance infrared Fourier transformation spectroscopy (DRIFTS). Instruments that use DRIFTS are conventional. 
   There are a plurality of apparati that can be used in accordance with the present invention. One such apparatus is a device which amounts to a single fiber-optic probe that has both a radiation source conduit and a detector conduit for collecting diffuse energy that focuses at the tip of the probe. To operate the probe, the sample is touched with the probe and illuminated with infrared radiation. The radiation is then absorbed by the gem and reflected by the gem as diffuse internal energy. This reflected diffuse internal energy is captured by the detector portion of the probe and then analyzed by the computer controlled detector array. Such NIR probes are conventional. Alternatively, the apparatus comprises a pedestal inside an integrating sphere (hollow sphere coated internally with a reflective diffusing material like SPECTRALON or diffuse gold coating). The NIR and MIR radiation is diffused and uniformly reflected from the walls of the sphere into the gemstone. The gemstone is mounted on the probe and the detection probe is mounted directly below the gemstone. Preferably, a transparent aluminum oxide sphere focuses the emerging energy onto the entrance of the fiber optic detection probe that is channeling the reflected diffuse internal energy to the detector array. 
   Suitable apparati that employ DRIFTS and can be used in accordance with the present invention include NICOLET MAGNA I R Series 760 and 860; BOMEN FT-NEAR IR Analysis; BIORAD FTIR 60A FTIR; NICOLET MAGNA Series 860; PERKIN ELMER LAMBDA 1C Spectrometer; and FOSS NIR System each with a diffuse reflector device (integrating sphere) from Spectratec, Pike Technologies, and Lapsphere. Such devices are operated in a conventional manner. 
   NIR probes are also conventional pieces of equipment which are operated in a conventional manner in order to accomplish the present invention. Suitable NIR probes can be obtained from Foss NIR System of Silver Spring, Md. and Nicolet Instrument Corporation of Madison, Wis. 
   Gems which can be subjected to the process of the present invention include all natural and synthetic gems such as diamonds, rubies, emeralds, sapphires, jade, turquoise, alexandrite, chalcedony, and pearl, as well as other gems that exhibit surface reaching fissure, fractures or porosity. Gems which can be subject to the present invention include not only those which have been cut and polished, but also those that are rough, i.e. not cut or polished. The main prerequisite for analysis is the presence of an “organic window” or non-absorbing areas in the spectral regions where organic materials exhibit characteristic spectral peaks. 
   Organic chemical compounds which can be detected by the present invention include both natural and synthetic compounds which have been used to enhance or alter the appearance of a gem. Such compounds include oils, waxes, and various natural and synthetic resins. Oils which can be detected by the present invention include, among others, cedar wood oil, That red oil, Canadian balsam, mineral oil, Indian dyed joban oil, clove stem oil, sesame oil and synthetic oil of wintergreen. Waxes and other solid/semi-solid fillers which can be detected by the present invention include shellac, carnauba and paraffin. Resins, polymers and prepolymers which can be detected by the present invention include PALMA, epoxy resin, EPON 828, CIBA-GEIGY 6010, OPTICON 224, as well as hardened and unhardened alternative resins. 
   The present invention can detect both single and multiple organic compounds. 

   
     BRIEF DESCRIPTION OF THE DRAWINGS 
     These and other aspects of the present invention may be more fully understood by reference to one or more of the following drawings: 
       FIG. 1  illustrates a conventional DRIFTS device as used in the process of the present invention; 
       FIG. 2  illustrates a NIR probe with a gem on top; 
       FIG. 3  illustrates a NIR probe having a gem attached thereto and immersed in a reflective solution; 
       FIG. 3A  is another embodiment of the present invention; 
       FIG. 3B  is another embodiment of the present invention; 
       FIG. 3C  is a top view of a probe in accordance with the present invention; 
       FIG. 3D  is a top view of another probe in accordance with the present invention; 
       FIG. 3E  is a top view of yet another probe in accordance with the present invention; 
       FIG. 3F  is a side view of another embodiment of the device illustrated in  FIG. 3 ; 
       FIG. 3G  is a side view of a device in accordance with the present invention that employs a focusing sphere; 
       FIG. 3H  is a side view of a device wherein an integrating cylinder is used; 
       FIG. 3I  is an end view of the integrating cylinder in  FIG. 3H ; 
       FIG. 4  illustrates a NIR spectra of pure epoxy resin; 
       FIG. 5  illustrates the absorbance of pure epoxy resin in the C-H first overtone region from  FIG. 1 ; 
       FIG. 6  illustrates the NIB absorbance spectra of an emerald sample containing no epoxy resin and an emerald sample containing an epoxy resin; 
       FIG. 7  illustrates the spectra for both the emerald containing epoxy resin and the emerald containing no epoxy resin of  FIG. 6 ; 
       FIG. 8  illustrates the average spectra for the emerald with epoxy resin and the clean emerald of  FIG. 7 ; 
       FIG. 9  illustrates the second derivative of the spectra for the emerald with epoxy resin and without epoxy resin of  FIG. 8 ; 
       FIG. 10  illustrates the average spectra for the emerald with epoxy resin and the clean emerald of  FIG. 9 ; 
       FIG. 11  illustrates the NIR spectra of pure epoxy resin, turquoise treated with epoxy resin, and untreated turquoise; 
       FIG. 12  illustrates the second derivative of the treated and untreated turquoise of  FIG. 11 ; 
       FIG. 13  illustrates an NIR spectra for emeralds, one which has been treated with epoxy resin and one which has been untreated; 
       FIG. 14  illustrates the second derivative of  FIG. 13  showing the treated and untreated emerald; 
       FIG. 15  illustrates an NIR spectra for pure That red oil; 
       FIG. 16  illustrates an NIR spectra for treated and untreated rubies; 
       FIG. 17  illustrates a DRIFTS spectra for a clean emerald; 
       FIG. 18  illustrates a DRIFTS spectra for an emerald treated with epoxy resin; 
       FIG. 19  illustrates a DRIFTS spectra for an emerald treated with a wax; 
       FIG. 20  illustrates a DRIFTS spectra for an emerald with an oil; 
       FIG. 21  illustrates a DRIFTS spectra for a clean ruby; and 
       FIG. 22  illustrates a DRIFTS spectra for a ruby treated with cedarwood oil. 
   

   DETAILED DESCRIPTION OF THE INVENTION 
   As illustrated in  FIG. 1 , a conventional DRIFTS device is illustrated which can be employed in the present invention. Source  10  is a source of infrared radiation. Source  10  emits radiation beam  12  which is deflected off of mirror  14  and directed to parabolic mirror  16  which, in turn, directs beam  12  to gem  20 . Gem  20  is contained on base  22  and in reflective cup  24 . Gem  20  reflects both specular and internal energy while cup  24  reflects internally transmitted energy, all of which are energy  30 . The reflected energy is captured by parabolic mirror  16  and reflected down to mirror  32  which, in turn, reflects it to detector  34  and detector  34  captures reflected diffuse internal energy. Analyzer  36  then performs a Fourier transformation on the captured data of the reflected energy in order to determine the presence or absence of organic chemical compounds. An analyzer  36  is suitably a conventional computer with the necessary software. 
     FIG. 2  illustrates the present invention for use with a probe. As depicted in  FIG. 2 , gem  40  is placed on top of probe  42 . Probe  42  has a center of fiber-optic core  44  which emits NIR radiation. Only reflected diffuse internal energy from gem  40  is captured by detectors  46  and then transmitted to analyzer  48 . 
     FIG. 3  illustrates another embodiment of the apparatus for use in the present invention wherein a total internal reflection immersion cell is employed. In this embodiment, gem  50  is held onto probe  52  by means of a holding device, shown as sealed vacuum cup  54 . Probe  52  with attached gem  50  is then immersed into reflective bath  56 . Bath  56  causes total internal reflection of NIR radiation. Thus, the detectors in probe  52  obtain reflected diffuse internal energy from gem  50 . Any radiation which would normally have passed outward through gem  50  is reflected back into gem  50  because bath  56  acts as a mirror to NIR radiation. In order to improve the spectrum, cooling unit  58  can be employed to cool bath  56  and gem  50 . Such cooling units are conventional and operated in a conventional manner to cool bath  56 . 
   Stabilizing the temperature of the measuring environment is important for consistent instrumental results. However, spectral features can be altered and/or enhanced by the application of temperature to the sampling environment. Cooling samples can in many instances accentuate spectral features. A thermocouple controlled temperature alteration device like a thermoelectric cooler and supplemental heating element placed on the outside of the total internal reflection immersion cell provide uniform cooling and heating of the sample by surrounding the sample with a uniform temperature controlled fluid environment. Alternatively, the immersion cell can be placed in a secondary chamber in order to be cooled with liquid nitrogen. 
   One of skill in the art can also use any type of reflective solutions that produce total internal reflection or apply an outside coating directly on the gem surface to produce total internal reflection. Reflective solutions and coating such as metal coatings include gold, silver, or any material that has an adjusted index so as to cause total internal reflection. 
     FIG. 3A  illustrates another embodiment where probe  60  with gem  62  is placed inside removable hollow sphere  64 . Sphere  64  has a diffuse reflective material  66  coating its inside surface. Probe  60  is identical to probe  42 . Removable sphere  64  rests on stop  68  and is removable with handle  69 . 
     FIG. 3B  illustrates another embodiment where IR detector channel  70  which leads to a detector is mounted in probe  71  on which gem  72  is mounted and placed inside hollow sphere  74  with diffuse reflective coating  76  therein. Sphere  74  has IR source  78 . Baffle  80  avoids the radiation directly hitting gem  72  and insures that diffuse radiation is used. 
   Suitable diffuse reflective coatings for spheres  64  and  74  are diffuse gold coatings, SPECTRALON®, and other suitable diffuse reflective coatings normally used in integrating spheres. 
   Suitable instruments for this process include LPM-040-SL and LPM-040-IG Laser Power Measurement Spheres manufactured by Labsphere of North Sutton, N.H. 
   An alternative to probe  42 ,  52  or  60  is a split probe in which one half of the probe is a detector and the other half of the probe is an IR source. A top view of such a split probe is shown in  FIG. 3C  wherein channel  90  leads to a detector and channel  92  leads to a radiation source. 
     FIG. 3D  illustrates a top view of another probe configuration in accordance with the present invention with multiple channels  94  leading to a detector and channel  96  provides radiation from a source. 
     FIG. 3E  illustrates a top view of the probe of  FIG. 3B . 
     FIG. 3F  is a side view of another total internal reflection immersion cell for immersing gem  100  in container  102  of reflective fluid  103 . Probe  104  is similar to the one shown in  FIG. 3C  with radiation channel  106  and detector channel  108  such that it acts as both an illuminator and a detector. Container  102  as inlet and exit ports  110  and  112  to allow fluid  103  to be filled and drained between tests. C-clamp  111  has a spring load top for holding gem  100  in place on probe  104  during testing. Fluid  103  can be liquid or a gas which provides total internal reflection to gem  100 . 
     FIG. 3G  illustrates a device  120  in accordance with the present invention wherein gem  122  sits on probe  124 . Channel  126  to the detector has an aluminum oxide focusing sphere  128 . IR source  130  is mounted in sphere  132  and baffled by baffle  134  to cause diffuse IR radiation throughout sphere  132 . The inside wall of sphere  132  has a diffuse reflective coating. 
     FIGS. 3H and 3I  illustrate yet another device  140  in accordance with the present invention. Device  140  has gem  142  mounted on probe  144 . Probe  144  has channel  146  to detector (similar to the device in  FIG. 3E ). Device  140  has integrating cylinder  150 , with a plurality of IR radiation sources  152 , each of which has baffle  153  for generating diffuse IR radiation in cylinder  150 . Cylinder  150  has its inside walls coated with a diffuse reflective material similar to the integrating spheres illustrated in  FIGS. 3A ,  3 B and  3 G. The advantage to device  140  is that multiple IR sources are employed, IR source  152  face blank walls, not each other. Also, working with a flat, rectangular exterior of cylinder  150  provides advantages. Port  154  provides access to cylinder  150 . 
   It should be noted that in the device of  FIGS. 3A ,  3 B and  3 G, it is preferred to have the gem at or near the center of the sphere or cylinder for best results. 
   These and other aspects of the present invention may be more fully understood by reference to one or more of the following examples. 
   EXAMPLE 1 
   This example illustrates using near infrared (NIR) and a probe to detect the presence of epoxy in an emerald. Two emeralds were analyzed, one of which contained a small amount of epoxy, and the other contained no epoxy. Both gems were approximately 5 mm in diameter. 
   As indicated in  FIG. 4 , a pure epoxy sample has a strong absorption, around 1700 nm. Peaks appeared at approximately 1648, 1670, 1698 nm (see  FIG. 5 ) and correspond to first overtone absorptions of C-H anticipated for epoxy (and not anticipated for emerald). 
   Absorbance spectra of the two emeralds are shown in  FIG. 6 . Although there are some differences (baseline and peak shape), no significant differences are seen at this scale in the region associated with strong epoxy absorbance. 
   In order to verify the presence or absence of epoxy in the spectra of the emeralds, two different mathematical treatments were evaluated. The first was a detrend treatment that consisted of a first order detrend correction (determine the best line through the data points, then subtract that line from the spectrum) from 1600-1730 nm, followed by a baseline correction to offset spectra to zero absorbance at 1654 nm, followed by a 10 point box car smooth. The resulting spectra are shown in  FIG. 7 . 
   Clear differences due to the epoxy absorbance can be seen in these spectra at approximately 1696, 1670 and 1644 nm. To further clarify the plots, all spectra of the same sample were averaged and the results are shown in  FIG. 8 . 
   As an alternative, second derivatives were generated from the raw spectra. Second derivative math treatments are commonly used in NIR since it eliminates baseline variations while enhancing band resolution. Second derivative plots are shown in  FIG. 9 . The maxima are inverted in this math treatment. Again, absorbances due to epoxy can clearly be seen (1,696, 1,668, 1,644 nm) in the individual spectra. 
   As before, individual plots were averaged to further enhance the results and these spectra are shown in  FIG. 10 . 
   As can be seen, diffuse reflection using NIR allowed for the detection of the organic compound (epoxy) in the emerald. 
   The NIR analysis was conducted in a conventional manner using conventional equipment. Specifically, the following technique was employed for this example and some of the following examples. 
   PTFE beads were added to the liquid sample (epoxy, oils) in order to effect sufficient reflectance for a useful spectrum. The spectra for the liquid sample was acquired with a RAPID CONTENT ANALYZER (RCA) (Foss NIR Systems, Silver Spring, Md.), which consisted of a model 6500 monochromator and a Rapid Content Module (both Foss NIR Systems). The dispersed light from a tungsten-halogen source is brought to the sample compartment by means of a fiber-optic bundle (420 fibers, each 200 μm diameter). This light then passes through the bottom of the vial (approximately 25 mm diameter) containing the liquid sample and PTFE beads and is then reflected back into the detector array of the Rapid Content Module, which consists of four PbS detectors and four Si detectors for collection of near-IR and visible spectra, respectively. Although transmission measurements through cuvettes were possible, use of this PTFE bead method allowed the use of disposable vials. This facilitated the handling of viscous samples. 
   Solid samples (wax and gems) were analyzed with the RCA (described above), SMARTPROBE ANALYZER (Foss NIR Systems), and/or INTACT TABLET ANALYZER (Foss Systems). Whenever sample size, permitted, gems were analyzed with all three analyzers in order to facilitate comparison of their spectra under different measurement conditions. Analysis of gems by the RCA consisted of simply centering each gem on the sampling area above the detectors. The SMARTPROBE ANALYZER consists of a model 6500 monochromator and a stainless steel fiber-optic bundle reflectance probe with 8-mm diameter sapphire window. The probe consists of two collinear fiber-optic bundles. Each bundle is 2 m long and is fabricated with 210 optic fibers (200 μm fiber diameter). One bundle transmits light from the exit slit of the monochromator to the sample. The reflected light from the sample is collected by the return fibers and is brought back to the analyzer for analysis by both a Si (400-1,100 nm) and PbS (1,100-2,500 nm) detector. Gems were measured by securing the probe in a vertical configuration (window facing up), placing the samples on the probe tip window, and positioning a light shield over the sample probe tip. 
   The INTACT TABLET ANALYZER consists of a Model 6500 monochromator and an Intact Table transmission module. The light from the exit slit of the monochromator passes through a fiber-optic bundle composed of 420 optic fibers (fiber diameter=200 μm, is transmitted by the sample, and finally is collected on an In GaAs detector (600-1,900 nm). 
   Each spectrum consists of 32 scans acquired at approximately 10 nm bandwidth, regardless of analyzer used. The gem samples were repositioned several times in order to optimize spectra. Digitized spectra were acquired and manipulated with the use of VISION software (Version 2.21) (Foss NIR Systems) or transferred to other data management software for processing. 
   EXAMPLE 2 
   This example illustrates using NIR diffuse reflective spectroscopy and a probe to detect the presence of epoxy in turquoise. 
   Turquoise beads were analyzed, one epoxy treated and one untreated. Both were tested according to Example 1 above.  FIG. 11  illustrates epoxy spectra A, treated turquoise (turquoise treated with epoxy) spectra B, and untreated turquoise spectra C. 
     FIG. 12  illustrates the second derivation spectra between 1,580 and 1,780 nm (where the C-H stretching overtones occur) for both the treated and untreated turquoise. 
   These tests were run in accordance with the procedure and equipment of Example 1 above. 
   As can be seen, the presence of the epoxy is detected. 
   EXAMPLE 3 
   This example illustrates using NIR diffuse reflectance spectroscopy and a probe to detect the presence of epoxy in emeralds, different than the sample used in Example 1 above. 
   Two emeralds were analyzed, one epoxy treated and one untreated. Both were tested according to Example 1 above. 
     FIG. 13  illustrates treated emerald spectra A, and untreated emerald spectra B. 
     FIG. 14  illustrates the second derivation spectra between 1,600 and 1,750 nm (where the C-H stretching overtones occur) for both the untreated A and treated emeralds B. 
   These tests were run in accordance with the procedure and equipment of Example 1 above. 
   EXAMPLE 4 
   This example illustrates using NIR diffuse reflectance spectroscopy and a probe to detect the presence of That red oil in rubies. 
     FIG. 15  illustrates the spectra for That red oil.  FIG. 16 . illustrates the second derivation spectra for a ruby treated with That red oil, curve A; and a clean, untreated ruby, curve B. 
   These tests were run in accordance with the procedure and equipment of Example 1 above. 
   As can be seen, the present invention allows for detection of the oil. 
   EXAMPLE 5 
   This example illustrates using the DRIFTS technique to detect the presence of organic fillers in emeralds. 
     FIG. 17  illustrates the DRIFTS spectra for a clean, natural 0.58 ct. Columbian emerald.  FIG. 18  illustrates the DRIFTS spectra for a 0.69 ct. emerald treated with an epoxy to fill the fractures. 
     FIG. 19  illustrates a DRIFTS spectra for a 1.32 ct. emerald treated with wax.  FIG. 20  illustrates a DRIFTS spectra for a 2.86 ct. emerald treated with an unknown oil approximately 20 years ago. 
   The C-H stretch band which determines the presence of an organic is around a wavelength of 2600 to 3000 cm −1 . 
   As can be seen, even small amounts of organic filler can be detected by the DRIFTS technique. In fact, the intensity of the C-H stretch band is a way to identify the type of organic filler. 
   The procedure and equipment used to conduct the DRIFTS analysis was conventional and similar to the device in  FIG. 1 . Specifically, the infrared windows made of potassium bromide were purchased from Aldrich. The infrared spectra of epoxy resin, oil and wax samples, the enhancers, were obtained using a NICOLET MAGNA-IR 750 spectrometer with a DTBS detector. The gem samples were analyzed using the same spectrometer equipped with a Spectra-Tech (Sheldon, Conn.) Baseline Diffuse Reflectance accessory. The accessory includes macro sampling cups made of polished stainless steel. The background was taken as a single-beam spectrum collected from an empty cup. After the alignment of the instrument and the accessory, the gem samples were placed in a macro sampling cup and inserted through the sample slide to the center of the accessory and infrared data were then collected. The position of the gem in the sampling cup was changed several times in order to maximize the C-H stretching bands. For larger samples which cannot be inserted directly using the sample slide, the alignment mirror was removed temporarily from its optimized position so a large entrance was available for the sample slide. After the gem sample was placed in the macro sampling cup and inserted to the center, the alignment mirror was returned to its optimized position and the data were then collected. All data were collected at 4 cm −1  resolution. Each spectrum was a result of 32 coadds, collected from 4,000 to 500 cm −1 . The data collected from the NICOLET computer were manipulated with the use of OMNIC FT-IR software or transferred to a PC for processing. 
   EXAMPLE 6 
   This example illustrates using the DRIFTS technique to detect the presence of cedarwood oil in a ruby. 
     FIG. 21  illustrates the DRIFTS spectra for a clean, natural 1.22 ct. ruby from Thailand.  FIG. 22  illustrates the DRIFTS spectra for a 9.34 ct. ruby that has been treated with cedarwood oil. 
   The DRIFTS technique used herein was the same as Example 5 above. 
   It will be understood that the claims are intended to cover all changes and modifications of the preferred embodiments of the invention herein chosen for the purpose of illustration which do not constitute a departure from the Spirit and scope of the invention.