spectral characteristics of natural-color saltwater

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&NBN TECHNIOUES SPECTRALCHARA TERISTI SOFNATURAL-COLOR SALTWATER ULTUREDPEARLSFROM PINCTADAMAXIMA StefanosKarampelas Natural-color saltwater cultured pearls (SWCPs) from Pinctadamaxima were studiedusing UV- Vis-NIRandPLspectroscopytobetter under- stand the mechanisms of their coloration and to separatethemfrom other SWCPswithsimi lar natural colors. Several spectral features were ob- served suggesting that the samples' bodycolor is due to amixtureof pigments.Althoughsimilar spectralcharacteristicsareobservedinSWCPs from Pteriasterna and Pinctadama r . garitifera subtle differences permit the identification of the host mollusk sa ltW culturedpearls from Pinc maXlma are farmed primarily in Australia as well as in In- donesia the Philippines Myanmar and other local- ities (see Shigley et a l ., 2010 and references therein). Marketed as"SouthSea"cultured pearls they are usuallybead-nucleatedandcanreachlargesizes (sometimes>20mm).The colorscommonlyfound inthe market rangefromwhiteto light gray("sil- ver to"cream" to yellow and "golden" (Elen 2001 200 2. b i Mamangkey et a l., 2010 j Shigley et al. 2010 and referencestherein).Lesscommonly theymay show pinkish purplish reddish or brown bodyco lors withvariousovertones(see figure1 andphotos in table1).The darker SWCPs from P maxima some- times appear similar to lighter-colored SWCPs from Pinctada margaritifera and Pteria sterna. The spectral characteristics of yellow to "golden" natural-color SWCPs from Pmaxima have been doc- See end of article for About the Author and Acknowledgments. GEMS & GEMOLOGY Vo l . 48 No.3 pp. 193-197 htp:ρ'dx.doi.orgl10.5741/GEMS .4 8.3.193. 2012Gemologi IInstitute of America NOTES & NEW TECHNIQUES urnented previously (El en 2001 2. 002b i Mamangkey et a l . 2010). This article presents a diffuse-reflectance and photoluminescence spectroscopic s tudy of natu- ral-color SWCPs from Pmaxima in an effort to char- acterize their coloration mechanisms. A better understanding of these mechanisms will help to iden- tify the Pmaxima host mollusk of South Sea cultured pearls and to separate natural-color samples from their artificially colored counte arts. MATERIAlS AND METHODS For this study the author selected 21 undr edSWCPs from Pmaxima in a range of colors (ag n see table 1). They were obtained from a r eputable source (see Acknowledgments) and represented as natural-color. The samples varied from 9.1to16.8 mm in diameterj for detailsontheir color and size seetable1.Their fluorescence was observed with a s ix-watt long- d Figure 1. Saltwater cultured pearls from the Pinctada maxima mo l1 usk (here 9.1-16.8 m m in diameter) may occur in a variety 01 attractive natural colors Composite photo by S. Karampelas. GEMS & G O 七悶Y F AlL 2012 193

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& NBN TECHNIOUES

SPECTRAL CHARA仁TERISTI仁SOF NATURAL-COLOR

SALTWATER仁ULTUREDPEARLS FROM

PINCTADA MAXIMA Stefanos Karampelas

Natural-color saltwater cultured pearls (SWCPs) from Pinctada maxima were studied using UV-Vis-NIR and PL spectroscopy to better under-

stand the mechanisms of their coloration and to separate them from other SWCPs with similar natural colors. Several spectral features were ob-

served, suggesting that the samples' bodycolor is

due to a mixture of pigments. Although similar spectral characteristics are observed in SWCPs from Pteria sterna and Pinctada mar.garitifera, subtle differences permit the identification of the

host mollusk

saltW仰 culturedpearls from Pinc附 maXlmaare farmed primarily in Australia, as well as in In-

donesia, the Philippines, Myanmar, and other local-ities (see Shigley et al., 2010, and references therein). Marketed as "South Sea" cultured pearls, they are usually bead-nucleated and can reach large sizes

(sometimes >20 mm). The colors commonly found in the market range from white to light gray ("sil-verつto"cream" to yellow and "golden" (Elen, 2001, 2002.bi Mamangkey et al., 2010j Shigley et al., 2010, and references therein). Less commonly, they may show pinkish, purplish, reddish, or brown bodycolors with various overtones (see figure 1 and photos in table 1). The darker SWCPs from P maxima some-

times appear similar to lighter-colored SWCPs from Pinctada margaritifera and Pteria sterna.

The spectral characteristics of yellow to "golden"

natural-color SWCPs from P maxima have been doc-

See end of article for About the Author and Acknowledgments. GEMS & GEMOLOGY, Vol. 48, No. 3, pp. 193-197, http:ρ'dx.doi.orgl10.5741/GEMS.48.3.193. 。2012Gemologi日 IInstitute of America

NOTES & NEW TECHNIQUES

urnented previously (Elen, 2001, 2.002bi Mamangkey et al., 2010). This article presents a diffuse-reflectance

and photoluminescence spectroscopic study of natu-ral-color SWCPs from P maxima in an effort to char-acterize their coloration mechanisms. A better

understanding of these mechanisms will help to iden-

tify the P maxima host mollusk of South Sea cultured pearls and to separate natural-color samples from their artificially colored counte叩arts.

MATERIAlS AND METHODS

For this study, the author selected 21 undr出edSWCPsfrom P maxima in a range of colors (agむn,see table 1). They were obtained from a reputable source (see Acknowledgments) and represented as natural-color.

The samples varied from 9.1 to 16.8 m m in diameterj for details on their color and size, see table 1. Their fluorescence was observed with a six-watt long-叩 d

Figure 1. Saltwater cultured pearls from the Pinctada maxima mol1usk (here, 9.1-16.8 mm in diameter) may occur in a variety 01 attractive natural colors Composite photo by S. Karampelas.

GEMS & G酬 O七悶Y FAlL 2012 193

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TABLE 1. Characteristics of natural-color SWCPs from P. maxima.

PhOIO Sample no. Bodycolor Dimensions (mm)

w GGL002 Yellowish brownish gray 9.3-9.9

~ GGL003 Yellowish brown 11.1

~ GGL004 Gray-purple 9.7

~必 GGL005 Gray 11.3

‘妙 「GGL006 Lighl gray-purple 11.8-12.3

~ GGL008 Gray (slightly brown) 10.6-11.4

⑫ GGL009 Reddish gray 9.1-9.4

@ GGL013 Grayish purple (Iight gray on the bottom) 10.3-11.8

、e GGL014 Gray-yellow-green 10.1-10.8

、. GGL020 Yellow-brown 11.7-13.7

@ GGL021 Gray-brown <lighter on the side) 15.1-16.8

、. GGL022 Gray 10.5-12.0

、設 GGL023 Light gray 10.6-12.2

@ GGL024 Gray-yellow-purple (Iighter on Ihe bottom) 13.8-15.8

、. GGL025 Gray 10.7時 12.0

'" GGL026 Gray-brown (Iighter on the bottom) 10.0-11.2

ゆ GGL030 Gray-brown-purple 10.3

司診 GGL033 Light purplish brown 9.7-10.1

ゆ GGL037 Light gray-pink 10.0

Q GGL043 Gray-pink 12.5

ゆ GGL044 Light gray-pink 11.3

字 Imagesnot scaled to size.

194 NOTES & NEW TECHNIOUES GEMS & GEMOLOGY FALL 2012

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UV-Vls-NIR REFLECTANCE SPECTRA ICO

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日♂lre3. Absorption bands at identical positions as in tgure 2, but with different relative intensities, are shown in the di所lse-reflectancιspectraof these four SWCP samples. The samples' color variation is due to the di庁er-ent relative intensities of these bands. For clarity, spectra GGL004 and GGL033 are shiβed downward by 15% and 5% respectively, and GGL044 upward by 5%

Fi♂lle 2. A gray-yellow-green SWCP (top line) shows absorptions at 280, 330-385, 385-460, 495, and a weak continuous absorption with a maximum at 820 nm, as well as less-intense features at 460,625, and 745 nm. Bands at the same positions but問 thdi庁er-ent intensities are observed in the spectra of reddish gray (middle) and gray-brown (bottom) samples. For clarity, the spectra for GGL009 and GGL014 are shifted upward by 5% and 25%, respectively.

spectrum of the gray-yellow-green sample (GGL014). An additional band at 495 nm and three shoulders at -460,625, and 745 nm are present. Bands at the same positions, but with different intensities, are seen in

• Saltwater cultured pearls (SWCPs) from P. maxima in a variety of natural colors were studied using UV-Vis-NIR and PL spectroscopy.

・η、eirbodycolors depend on the relative intensity of up to six absorptions, which are probably determined by various combinations of several pigmen包.

• Natural-color SWCPs from P. marga刈た'raand Pteria sterna show similar absorption and PL bands, but their UV-Vis-NIR spectra also show a 405 nm band that is not seen in those from P. maxima.

• An additional band at about 700 nm is known only from P. margariti耐 aSWCPs, while Pteria sterna SWCPs display more-intense PL bands and charaderis-tic red fluorescence to long-wave UV radiation.

the spectra of samples GGL009 (reddish gray) and GGL021 (gray-brown).

Figure 3 presents diffuse-reflectance spectra of four

differently colored SWCPs: light gray pink, graぁlightpurplish brown, and gray-purple. These have abso中ー

In Brief

short-wave (365 and 254 nm, respectively) UV lamp.

UV-Vis-NIR spectra were obtained for all samples using a Cary 5000 spectrometer fitted with a Varian diffuse-reflectance accessory. The parameters used

were identical to those presented by Karampelas et al. (2011a). Photoluminescence (PL) spectra of all the samples were acquired using a Renishaw Raman 1000

spectrometer coupled with a Leica DMLM optical mi-croscope using 50x magnification, with叩 excitationwavelength of 514 nm emitted by an argon-ion laser

凶川,a power of 10 m W, a lO-second acquisition tirne, and a resolution of about 0.1 nm. The results were compared to previously published studies of natural-

color SWCPs from P margaritifera釦 dPteria sterna.

RESULTS AND DISCUSSION

Figures 2 and 3 show the diffuse-reflectance UV-Vis-NIR spectra from 250 to 900 nm for seven natural-

color P maxima SWCPs. Each features an absorption (i.c., a decrease in diffuse reflectance) at about 280 nm. In figure 2, each sample shows a region of con-

tinuous absorption centered at -820 nm (in the near-infrared) that gradually absorbs through the visible region (i.e., 390-780 nm). An absorption from the UV

to the blue region, consisting of two bands centered at about 330-385 and 385-460 nm, is observed in the

195 FALL 2012 GEMS & GEMOLQGY NOTES & N町 TECHNIOUES

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PHOTOLUMINESCENCE SPECTRA

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Figure 5. The photoluminescence spectra of three dif-ferently colored SWCPs from P. maxima show bands at 620, 650, and 680 nm. The sharp features at 520 and 550 nm are due to the Raman e庁ιct

organic matrix between the aragonite p1ate1ets that constitute the nacre (Snow et a1., 2004).

Fi♂lre 5 presents PL spectra of three different-co1-ored P maxima SWCPs (GGL009, GGL021, and GGL044). PL bands in the orange-to・redregion at -620, 650, and 680 nm are present in each of the spectra. Simi1ar PL bands have been observed in nat-ura1-co1or SWCPs from P margaritifera and Pteria sterna (Miyoshi et a1., 1987; Kiefert et a1., 2004; Karampe1as et a1., 2011b). None of these bands could be attributed to a known pigment. Under short-and 10ng-wave UV radiation, the light-colored samples in the present study were inert, while the others showed a weak greenish yellow and weak yellow re-action, respectively. Simi1ar 1uminescence has been observed in some natural-color cultured pearls from P margaritifera (Elen 2002a; Wang et a1., 2006). How-ever, the vast majority of SWCPs from Pteria sterna exhibit red fluorescence to 10ng-wave UV radiation; some dark natural-color SWCPs from P margari-tifera exhibit wcak red luminescence as we11(Kiefert et a1., 2004).

tions simi1ar to those ,pbserved in figure 2. The same six absorptions in the visible region紅 eobserved in a11 the samples; only their relative intensity varies. Their specific colors are due to the different relative inten-sities of these bands. Absorptions at identical posi-tions are observed in natura1-color SWCPs from P margaritifera and Pteria sterna (Karampelas et a1., 2011a,b). An additional absorption at 405 nm often oc-curs in natural-color SWCPs from P margaritifera and Pteria sterna, and another at 700 nm appears only in natural-color SWCPs from P margaritifera (fi伊 re4).

A total of six absorptions in the visib1e region are observed in SWCPs from P maxima. Each sample's bodyco1or depends on the relative intensity of these absorptions, which are probab1y determined by vari-ous combinations of several pigments (as many as s民).To date, none of these six absorption features has been attributed to a specific pigment. The absorption from the UV to the blue portion of the e1ectromagnetic spectr~m (330-460 nm) has been documented in nat-ura1-color yellow to "golden" cultur吋 pear1sfrom P maxima (Elen, 2001,2002b; Mamangkey et al., 2010). Light gray, "cream/' and "golden" natural colors of SWCPs from P maxima have been associated with di丘erentthicknesses of the edge band structures, the

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Figure 4. UV-Vis-NIR di所lse-reflectancespectra are shown for gray natural-color SWCPs from threeゐffer-ent mo11usks. Similar absorptions are observed in a11 three spectra. An additional absorption at 405 nm is observed in the spectra of P. margaritifera and Pteria sterna SWCPs, and another at 700 nm appears in those from P. margaritifera. For clarity, spectra t示。mP. mar-garitifera and Pteria sterna are shif也ddownward by 30% and 15%, respectively.

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SWCPs from P maxima have a variety of natural bodyco1ors (e.g., fi忽rre6) due to the relative intensity of several absorptions in the visible range. They a1so display three PL bands in the orange-to-red portion of the electromagnetic spectrum. Natura1-color SWCPs from P margaritifera and Pteria sterna show absorp-

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FALl2012 GEMS & GEMOLOGY NOTES & NEW TECHNIOUES 196

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tion and PL bands similar to these. However, SWCPs

from P margaritifera and Pteria sterna exhibit a 405 nm band that has not been observed in specimens

from P maxima. Moreover, an additional band at about 700 nm is known only from P margaritifera

SWCPs. Samples from Pteria sterna display more-in-

tense PL bands and a red fluorescence to long-wave

ABOUT THE AUTHOR

Dr. Karampelas ([email protected]) is a research scientist at the Gubelin Gem Lab in Lucerne, Switzer/and.

REFERENCES

Elen S. (2001) Spectral reflectance and fluorescence characteristics of natural-∞lor and heat-treated "golden" South Sea cultured pearls GfJJG, Vol. 37, No. 2, pp. 114-123, http://dx.doi.orgJlO.5741/ GEMS.37.2.114.

一一一-(2002a) Identification of yellow cultured pearls from the black-lipped oyster Pinctada margaritifera. GeJG, Vol. 38, No 1, pp. 66-72, http://dx.doi.org/1O.5741/GEMS.38.1.66

一一- (2002b) Update on the identification of treated "golden" South Sea cultured pearls. Cfj)C, Vol. 38, No. 2, pp. 156-159, http://dx.doi.org/1O.5 741/GEMS.38.2.156.

Karampelas 5., Fritsch E., Gauthier J-P., Hainschwang T. (2011a) UV-Vis-NIR reflectance spectroscopy of natural-color saltwater pearls from Pinctada margaritifera. Cfj)C, Vol. 47, No. 1, pp. 31-35, http://dx.doi.orgJI0.5741/GEM5.47.1.31

Karampelas 5., Fritsch E., Hainschwang T., Gauthier J・P.(2011b)5pectral differentiation of natural color saltwater cultured pearls from Pinctada margariti!,ιra and Pteria sterna. Cfj)C, Vol. 47, No. 2, p. 117, http://dx.doi.org/1O.5741jGEMS.47.2.117.

Kief巴rtL., Moreno D.M., Arizmendi E., Hanni H.A., Elen 5. (2004) Cultured pearls from the Gulf of California, Mexico. CfJJC, Vol 40, No. 1, pp. 26-39, http://dx.doi.org/1O.5741/GEM5.40.1.26.

NOTES & NEW TECHNIOUES

Figure 6. This bracelet features a round grayish pink 12 mm saltwater cultured pearl, repre・sented as having natural color, from P. maxima. Photo @Autore

UV radiation that is not observed in SWCPs from P maxima and seen only rarely in those from P mar・

garitifera. None of these PL and absorption bands

have been attributed to a known pigment. Further re-

search using destructive means on isolated natural

pigments found in SWCPs from P maxima is needed

to identify the立exactnat山 e.

ACKNOWLEDGMENTS

The author is grateful to the Autore Group (Sydney. Australia) for providing the samples for this study.

Mamangk巴yN.G.F., Agatonovic 5., 50uthgate P.C. (2010) Assessー

ing pearl quality using reflectanc巴 UV-Vis spectroscopy: Does the same donor produce consistent pearl quality? Marine Drugs, Vol. 8, No. 9, pp. 2517-2525, http://dx.doi.org/l0.3390/ md8092517.

Miyoshi T., Matsuda Y., Komatsu H. (1987) Fluorescence from pearls and shells of black-lip oyster, Pinctada margariti!era, and its contribution to the distinction of mother oysters used in pearl culture. fapanese fournal of Applied Physics, Vol. 26, No. 7, pp. 1069-1072, http://dx.doi.org/1O.1I43/JJAP.26.1069

Shigley j.E., Laurs B.M., Janse A.j.A., Elen 5., Dirlam D.M. (2010) Gem localities of the 2000s. GeJC, Vol. 46, No. 3, pp. 188-216, http://dx.doi.org/ 1 0.5 741/GEMS.46.3.188.

5now M. R., Pring A., Self P., Losic D., Shapter J. (2004) Thc origin of the color of pearls in iridescence from nano-composite Struc-tur巴Sof the nacre. American Mineralogist, Vol. 89, No. 10, pp 1353-1358.

Wang w., Scarratt K., Hyatt A., Shen A.H.-T., Hall M. (2006) lden-tification of "chocolate pearls" treated by Ballerina Pearl Co CeJG, Vol. 42, No. 4, pp. 222-235, http://dx.doi.org/l0.5741/ GEMS.42.4.222.

GEMS & GEMOLOGY FALL 2012 197

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