Pigmentation in N. grubei K. Carlson Abstract Pigmentation in the polychaete worm Nereis grubei has two components. The dark green bile pigment biliverdin occurs in granules in the body wall and in the coelom. An unidentified blue-green pigment was found in the body wall and in oocytes of spawning females. Protective coloration is enhanced by both biliverdin and the unknown pigment. Structural differences appear to be responsible for the color change during oocyte maturation in Nereis grubei. igmentation in N. grube K. Carlson Introduction Theevivid green color of the polychaete worm Nereis grubei during its spawning season has been noted by many authors (Reish 1954, Schroeder 1968). Gould and Schroeder (1968) observed an oocyte color change of blue to yellow green during matura¬ tion. During this time the color of oocytes tends to dom¬ inate the normal year-round darker green color of the body wall. The purpose of this work is to determine the nature of the colored pigments in spawning females of Nereis grubei. Materials and Methods Nereis grubei containing eggs were collected in gastro¬ clonium holdfasts at Hopkins Marine Station and Stillwater Cove, Monterey County, California. Eggs were removed from forty worms by pipette and their bodies cleaned by washing with Instant Ocean. Both body wall and eggs were frozen un- til used. The body walls were extracted with cold acetone (5°C) while grinding, yielding an orange solution. A green color remained. The procedure of Bingham (1975) was followed in attempting to purify the orange body wall extract. Spectra were taken in acetone with a Beckman DK-2A spectrophotometer, Tests of H,SO, addition (Fox 1953), SbCl3 addition (Fox,Crane, and McConnaughney 1948), and staining by Sudan Black B (Work and Work 1969) on filter paper were used. The unknown pigment Pigmentation in N. grubei K. Carlson was chromatographed on 500 preparative silica plates with fluorescent-indicator and developed with 25% acetone in hex¬ ane. Relevant tests and spectra were obtained from the de- veloped bands. The green pigment remaining was extracted with 5% HOl in methanol to give in solution a bright green color. This green solution was extracted into chloroform by addition of water. The Gmelin reaction (Fox 1953), zinc acetate-iodine test (With 1968), and conc. HoSOp destruction were carried out. Spectra were obtained in acidified methanol. Only blue colored eggs were used for extraction. They were rinsed over a glass filter and ground with distilled water. When rinsed the eggs immediately turned to yellow-green. Removed to a phosphate buffer (KHoPOL and Na»HPOL) pH 7 ac¬ cording to the procedure of Lee (1966) followed by centri¬ fugation (Gilchrist 1968) failed to extract the pigment in- to the aqueous solution. Acetone was added, yielding a clear yellow solution; repeated extraction removed all color from residue. A preliminary drying was carried out with sodium sulfate. Purification and characterization were done as with the body wall orange pigment. Results The green color of N. grubei has two components: a darker color found in the body wall and in particles within the coelom, and a blue-green color found in both the body Pigmentation in N. grubei K. Carlson wall and eggs of spawning females. These colors were extrac¬ ted and analyzed separately. The darker color was found to be biliverdin, as Dales (1954) found in Nereis diversicolor, and the blue-green color was due to unidentified pigments ex¬ hibiting many properties of the chromolipoids. Dark green pigment of body wall: The spectrum in 5%HCl/ methanol gave the following peaks: 369 sharp 690-700 broad This absorption closely resembles the spectrum of known biliverdin (Sigma Chemical Company, St. Louis, Mo.). Both spectra are shown in Fig. 1. The Gmelin test for bile pig- ments was positive and a red fluorescence indicating a bila¬ triene was obtained after addition of zinc acetate and iodine. Destruction by conc. HoSOp distinguished this pigment from mesobiliverdin. The biliverdin pigment in N. grubei occurs as granules of varying sizes, often 9-10u, throughout the body wall. Con- centrations of biliverdin are found anteriorally, the dorsal side. This is in contrast to Dales (1954) who found less biliverdin in this area and instead a darker color due to carotenoids. Also, large (usually 2504) particles of very concentrated pigment were found free in the coelom. When the green color was dissolved away from these particles mucous like fragments remained. Most probably these are coelomic Pigmentation in N. grubei K. Carlson cells (Dales 1954). Granule sizes found in N. grubei are an an order of magnitude greater than those found by Dales in N. diversicolor. Extracted orange pigment of body wall: This pigment gave a negative Gmelin reaction and was soluble in acetone, hexane, chloroform, slightly soluble in ethanol, and insol¬ üble in water. The spectrum obtained in acetone is shown in Fig. 2. In hexane under UV (Black Ray UVL 21, Ultraviolet Products Inc.) the pigment gave a bluish fluorescence on the top layer and a green fluorescence in a lower layer. Addition of conc. H,SO gave a color change from yellow to cloudy orange, not the blue or green characteristic of car¬ otenoids. Addition of SbCla also failed to give a blue re¬ action and instead cloudy orange. The pigment was stained by Sudan Black B. Chromatography (25% acetone in hexane) revealed four colored bands with the Re values shown in Fig. 3. In hexane all solutions were pale yellow, band two (Re 0.46) was the most highly colored. Viewed in ultraviolet light the chromatograph revealed extensive fluorescent impurities throughout the eluted zone. Fluorescence varied from green and blue to a bright purple band between bands two (Rg 0.46) and one (Rg 0.34). The data and tests obtained from the chromatograph after elution with methanol are given in Table 1. The control is Pigmentation in N. grubei K. Carlson from material eluted from an undeveloped silica gel plate. Pigment of Oocytes: Yellow-green eggs collected from a small number of N. grubei when frozen turned reversibly to the blue color of the less mature oocytes. After extraction of the blue colored eggs the yellow solution in acetone gave the absorption spectra shown in Fig. 2. Under ultraviolet light the hexane solution fluoresced whitish purple. Addition of conc. HoSO,, gave a change of yellow to cloudy orange. Addition of SbCl, yielded an orange brown solution. The pigment was stained by Sudan Black B. Co-chromatography with the unknown body pigment revealed identical bands both in visible and ultraviolet light. Discussion The biliverdin in N. diversicolor was found by Dales (1954) to be derived from hemoglobin. Considering the sim¬ ilarities of occurence it seems reasonable to assume the same derivation for the biliverdin found in N. grubei. It is not known whether the amount of biliverdin in N. grubei increases in sexual epitoky during the spawning season as in N. diversicolor. The large particles found in the coelom seem to indicate that large amounts of biliverdin are in the pro- cess of being removed to the gut (Dales 1954). In N. diversicolor Dales (1954) found a darker area dorsally and anteriorally, due to carotenoids, and speculated its role was protective coloration. It is interesting to note Pigmentation in N. grubei K. Carlson that the same area is darkened by N. grubei, although in this case colored by biliverdin. Protective coloration seems likely. Shorebirds were seen feeding in the algal fields from which N. grubei were collected. The biliverdin matches well with the light to dark green color of gastroclonium holdfasts. Though gastroclonium was found to vary in color from yellow- green to dark green to brown, its holdfasts retained the same green color. During the spawning season (February to June when females become a noticable bright blue-green, Schroeder (1968) found an N. grubei migration to gastroclonium from the brown colored kelp Egregia menziesii. Migration to a protectively colored environment is well correlated with color development by spawning females. The oocyte color change during maturation seems to be the result of structural differences in the tissues. Along with this color change Gould and Schroeder (1969) found in¬ tensive stratification of the cytoplasm in mature oocytes. Evidence presented here, based on co-chromatography and spectral similarities, indicates that the blue-green color in body wall and oocytes of N. grubei results from the same pigments. Because of impurities, I was unable to satisfactorally characterize the blue-green color of body wall and eggs of N. grubei. After chemical tests, insufficient color remained to purify by re-chromatographing. Experiments with controls Pigmentation in N. grubei K. Carlson of known carotenoids gave negative tests for carotenoids when combined with the unknown pigment. Carotenoids may be pre¬ sent and not detectable because of inadequate purification. Yet the green color (a possible carotenoprotein) would neither extract with water nor buffer solutions, both used to extract green carotenoproteins. (Cheesman, Lee, Zagalsky 1967). The same argument of insufficient purification holds in the attempt to characterize the unknown as chromolipoids. In this case, however, many tests (solvent solubilities, conc. HSO. SbCl3, and Sudan Black B staining) indicate their pre- sence. It is not known what effects impurities would have on chromolipoid detection. Yellow chromolipoids in the poly¬ chaete Thoracophelia mucronata were found by Fox, Crane and MoConnaughney (1948). A green chromolipoid was found by Tessier (1929) in a number of hydroids. It is not known whether a chromolipoid could be responsible for a green color and subsequent change to yellow with acetone extraction. Sterols are known to absorb in ultraviolet light and though these should have been removed by saponification. their presence may be responsible for the high spectral absorption in the ultraviolet region. . Pigmentation in N. grubei K. Carlson Summary Pigmentation in the polychaete worm Nereis grubei has two components. The dark green bile pigment biliverdin occurs in granules in the body wall and in the coelom. An unidentified blue-green pigment was found in the body wall and in oocytes of spawning females. Protective coloration is enhanced by both biliverdin and the unknown pigment. Structural differences appear to be responsible for the color change during oocyte maturation in Nereis grubei. HCHME LINE COTTONF 0 Sigmentation in N. grubei K. Carlson Acknowledgements To Dr. Frederick A. Fuhrman for his time, advice, and constant help. 10 Pigmentation in N. grubei K. Carlson References Bingham, Alpheus, 1975. Amphibian carotenoids: Occurence of Lutein in Agalychnis dacnicolor. Unpublished re- search report No. 2. Department of Chemistry Stanford University. Cheesman, D. F., W. L. Lee and P. F. Zagalsky 1967 Carotenoproteins in Invertebrates. Biol. Rev. 42: 132-160. Dales, R. P. and G. Y. Kennedy. On the diverse colors of sicolor. J. Mar. Biol. Ass. U.K. Nereis diver 33: 699-708. Fox, D. L., 1953. Animals Biochromes and Structural Colors, Cambridge University Press, pp. 191, 273. Fox, D. L., S. C. Crane and B. H. McConnaughey, 1948. A Biochemical Study of the Marine Annelid Worm, Thoracophelia mucronata. J. Mar.Res. 7:567-85. Gilchrist, B. M., 1968. Distribution and relative abundance of carotenoid pigments in Anostraca (Crustacea: Branchiopoda). Comp. Biochem. Physiol. 24: 123-147. Gould, M. C., and P. C. Schroeder, 1969. Studies on oogenesis in the polychaete annelid Nereis grubei. Bio. Bull. 136: 216-225. Lee, W. L., 1966. Pigmentation of the Marine Isopod Idothea granulosa (Rathke). Comp. Biochem. Physiol. 19: 13-27. Reish, Donald J., 1954. The Life History and Ecology of the Polychaetous Annelid Nereis grubei. Allan Hancock Found. Publ. Occas. Pap. No. 14: 1-74. Schroeder P. C., 1968. On the life history of N. grubei, a polychaete annelid from California. Pac. Sci. 22: 476-481. Teissier, G. and M. Volkonsky, 1929. Bull. Soc. zool. Fr. 54: 599. With, Torben K., 1968. Bile Pigments, Academic Press, p. 13. Work, T. S. and E. Work, 1969. Laboratory Techniques in Bio- chemistry and Molecular Biology, Vol. I, John Wiley and Sons Inc., p. 531. 11 12 Pigmentation in N. grubei K. Carlson Captions Fig. 1 Absorption Spectra of Unknown and Known Biliverdin. Solvent: 5% HCl/methanol. Absorption Spectra of Unknown Oocyte and Body Fig. 2 Wall Pigments in N. grubei. Solvent: Acetone. Fig. Chromatograph of Extracted Orange Pigment in N. grubei. Table 1 Eluted Bands from Chromatograph of the Orange Pig- ment in N. grubei. Fig. 4 Absorption Spectra of Eluted Bands from Chromatograph of the Orange Pigment in N. grubei. Solvent: Hexane. E S 0TTO — e — — 8 Re.9 Rf.-46 Rf.34 origin fig.3 — I solvent front pale yellow ellow pale orange pale orange N — E N N N e Ge N N 08 2 7 0 + s — Der 5