Abstract The purpose of this experiment was to determine if there is a relationship between lowered nitrate levels in seawater and subsequent degradation of phycobilins in Rhodymenia pacifica when grown under adequate light. Phycobilins, accessory photosynthetic pigments, are often degraded under nitrate stress because of their high nitrogen content. In this experiment, the subtidal red alga R. pacifica was placed in tanks of artificial seawater with varying nitrate concentrations (0, 10, and 20 uM), and the phycobilin levels of these thalli were traced over five weeks. Phycobilin levels in the thalli in all treatments decreased significantly among weeks and treatments. Thalli given no nitrate had lower phycobilin levels than the 10 and 20 uM treatments, whose levels decreased at approximately the same rate. Additional thalli were grown in natural seawater with identical experimental conditions; their phycobilin levels decreased less markedly over time. All thalli except for those in natural seawater began to turn green at their tips after approximately two weeks; this green tissue was very weak and degraded when it was touched. Chlorophyll a levels of all samples remained constant throughout the experiment, and there was no growth of any thalli. Elemental analysis of the tissues was performed; there was a significant increase in percent carbon in all treatments over time, but no significant changes in percent nitrogen. In conclusion, there is a definite trend which shows that decreased nitrate concentrations do lower phycobilin concentrations over time. However, there presence of green thalli tissue suggests that there may have been other factors involved as well. Introduction This experiment examined the relationship between phycobilin concentration in Rhodymenia pacifica, a red algae, with nitrate levels in the ambient seawater. Nitrogen and light intensity are the two limiting factors for algal growth in the ocean. When nitrate concentration of the ambient water is low, both cyanobacteria (blue-green algae) and red algae are faced with a tradeoff. If the light intensity is very low, the algae need all of their phycobilins to capture enough light for photosynthesis so that they may survive. However, if the light intensity is strong enough, the algae can afford to degrade some of their phycobilins, which are nitrogen rich accessory photosynthetic pigments. Nitrogen from the phycobilins is used in other metabolic functions, such as growth and regulating enzymes involved in photosynthesis (Hanisak, 1983). Because the main absorbance ranges of phycobilins are in regions of light where chlorophyll cannot absorb, the degradation of these pigments affects the thallus' ability to use those other wavelengths (Gannt, 1990). The degradation of phycobilins causes the tissue to change from a deep red or blue-green (for red algae and cyanobacteria, respectively) into either a lighter red-yellow or a light green-yellow, depending on the species and the level of nitrate stress (Collier, 1992) Several studies of cyanobacteria and red algae have examined the effects of nitrate stress. When the cyanobacterium Synechococcus was deprived of nitrogen, it rapidly turned to a bleached yellow as its phycobilins were degraded. Cell growth slowed dramatically, and there was no synthesis of new chlorophyll molecules (Collier, 1992). In the red alga Corallina elongata, phycobiliprotein synthesis occurs under low irradiance only when there is sufficient nitrogen present. Conditions of saturating irradiance and limiting nitrogen resulted in degradation of the phycobilins (Vergara, 1993a). In other work with Gelidium sesquipedale, Vergara (1993b) found that phycobilins were an internal nitrogen reserve for the algae and that the concentration of these pigments was related to ambient nitrate levels. It should be noted that red algae are not capable of fixing elemental nitrogen, they must obtain nitrogen in the form of nitrate (NÖ3) or ammonium (NH4) (Hanisak, 1983). Absorbed nitrate and ammonium are rapidly used once absorbed; there is less than 1 umole-cm-3 in the cytosol of red algae (Reed 1990). There are several phycobilins present in red algae; variation in the relative amounts of each result in different thalli colors for different species. In nearly all species, the phycobilins are abundant enough that they mask the presence of chlorophyll a. Unlike chlorophyll, however, these pigments are water soluble and are attached to a protein; thus the name a phycobiliprotein. These are grouped together as phycobilisomes on the outer surfaces of the thylakoid membrane in chloroplasts (Bold & Wynne, 1978). During El Nifio years, it has been observed that Rhodymenia pacifica in shallow (7m) water changes from its deep red hue into a sickly yellow (J. Watanabe, personal comm.). El Nifio conditions result when the nutrient poor ocean surface layer is deeper than usual; thus when upwelling occurs, only the surface water is recirculated. This results in warmer, nutrient poor water along the California coast. El Nifios occur approximately every five years, so this phenomenon is very significant in the life cycles of most marine organisms. Thus, the primary purpose of this experiment was to determine whether bleaching of Rhodymenia thalli occurred as a response to nitrate limitation or as a response to other factors, including increased temperature and/or light. In particular, by maintaining water at the same temperature as ambient seawater and giving the thalli sufficient light, the effects due to nitrate stress alone could be measured. Rhodymenia is a slow growing subtidal red algae which is common off the coast of Central California. Thalli of this species grow to several centimeters in length, and by the end of the summer they are overgrown with small invertebrates such as bryozoans and polychaetes. Rhodymenia grows in large clusters attached to rocks on the ocean floor. Rhodymenia thalli were collected and then grown in artificial seawater with differing amounts of nitrate so that the concentration of phycobilins over time could be determined through simple extractions of the pigments. The most abundant phycobiliprotein by far in Rhodymenia is R-phycoerythrin; thus, the levels of this pigment were tracked over time. By measuring factors such as chlorophyll content, growth, and percent carbon and nitrogen, as well as R phycoerythrin over the course of a month, it was hoped that trends in some or all of these would become apparent as thalli were subjected to varying levels of dissolved nitrate. Materials and Methods Algae Collection and Culture Rhodymenia pacifica thalli were placed in twelve clear plastic tanks " and these tanks were which had base dimensions of approximately 13", covered with clear thin plastic sheets. Each tank contained approximately twenty grams wet weight of thalli, immersed in three liters of either artificial seawater with one of three known concentrations of nitrate (0, 10, 20 uM) or natural seawater with ambient levels of nitrate (approx. 20 uM). There were two replicates per treatment. Thalli were collected during April 1994 by using SCÜBA at depths of 6.5m (referred to as "pale") and 10m ("dark") from the Hopkins Marine Life Refuge (HMLR) in Pacific Grove, CA. There was a slight but noticeable difference in the colors of the thalli at different depths; shallow (pale) specimens were a lighter red than their deeper (dark) counterparts. Thus, these were placed in separate tanks. Dark thalli were placed in tanks with 0, 10, and 20 uM NÖg as well as in natural seawater. Pale thalli were placed in tanks with 0 or 20 uM NO3. The artificial seawater was made from Sigma’s Sea Salts and Provasoli’s enrichment solution (Carolina Biological Supply, Technical Report). At the end of the month, additional thalli were harvested from 6.5m and 10m at approximately the same locations as experimental thalli to determine their pigment concentrations. During the spring, ambient levels at the HMLR range from 20 to 25 uM NO3 (Watanabe & Phillips, unpubl. data). Three times, prior to daily addition of nitrate, water samples were taken from selected experimental tanks and frozen for later nitrate analysis. All tanks were immersed in ambient-temperature running natural seawater; this ensured that the tanks' water temperature was never more than 2°C higher than the surrounding water, which varied from 12 to 13°C. The artificial seawater was changed every four to five days, with nitrate added daily. The average nitrate uptake rate was estimated to be half of the Vmax for Gracilaria, a red algae, from Hanisak (1983), and all nitrate in a tank was assumed to have been used in twenty-four hours. These rates were used to estimate quantities of nitrate that were required to maintain the desired experimental conditions. Each morning, nitrate was added to tanks so that the initial concentrations were 40 uM or 20 uM. Thus, the daily average concentrations were 20 uM or 10 uM. Small air stones were placed inside each tank to maintain adequate mixing of the water. Shade cloth was placed on top of all of the tanks so that the maximum light intensity that the algae experienced was not more than 400 uEm-2s-1, which is slightly lower than the maximum light intensity at 10m deep over the past three years at HMLR (Watanabe & Phillips, unpubl. data). Most thalli in the tanks had small amounts of fouling organisms growing on them; sections of the thalli with these organisms were not used in any of the procedures listed in the following sections. Extraction of Pigments Tissue samples were taken weekly from each tank and analyzed for chlorophyll and phycobiliprotein content in the following manner. For chlorophyll extractions, approximately 1.5g of tissue was frozen in liquid nitrogen, ground in a mortar and pestle, and then ground for ten to fifteen minutes in a ground glass tissue grinder with 4ml acetone. The resulting mixture was spun until the supernatant was no longer cloudy. It was analyzed in a Hewlett Packard 8452A diode array spectrophotometer, and the concentration of chlorophyll was determined according to Jeffrey and Humphrey (1975). Phycobiliproteins were extracted from 0.25 g of tissue and then frozen in liquid nitrogen, ground in a mortar and pestle, and then ground with 4ml of O.1M phosphate buffer, pH 6.8 until no color remained in the tissue fragments. Concentration of R-phycoerythrin, the main phycobiliprotein in Rhodymenia, was determined from absorption data from the spectrophotometer (Lobban et al, 1988; Beer & Eschel, 1985). After several weeks, it became clear that pigment loss was occurring mostly at the tips of the thalli, rather than uniformly across the thalli. Thus, samples for week four were taken specifically from the tips. Other Procedures One plant from each tank was tagged and its blotted wet mass was taken weekly to determine growth rates. At the end of the month, the condition of all remaining thalli was determined by estimating by eye the percent of algae which had turned from a thick, deep red into a thin, sickly green in each tank. This was to provide an independent measurement of the degradation of phycobilins by Rhodymenia. At weeks zero, two, and four, one to two grams of tissue were dried overnight at 60’C, ground, and placed in a Leeman Labs 240XA elemental analyzer to determine the percent composition of carbon, hydrogen, and nitrogen for each sample. Data Analysis Data were analyzed by a two-way ANÖVA with time and NO3 concentration as fixed factors. Results Growth and Appearance of Thalli Over the course of a month, there were several noticeable changes in the appearance of Rhodymenia thalli in tanks with artificial seawater. Although the thalli in the two tanks with natural seawater did not show any visible differences in color or texture; thalli in all other tanks began to turn green at the growing tips. The green tissue then slowly spread down the thalli. This green tissue was much thinner and disintegrated easily when touched. Consequently, the tissue samples which were weighed each week remained constant or decreased in mass as the green tissue broke off of the thalli (Fig. 1). As a result, there was little or no growth of thalli during the course of the experiment. At the end of the experiment, each tank was analyzed for percent of thalli which had turned a sickly green (Fig. 2). It should be noted, however that none of the algae was green at the beginning of the experiment. During the course of the experiment, the dark and the pale thalli which had not yet turned green became indistinguishable in color. The dark thalli's color faded slightly so that it became the same shade as the pale thalli Assays of Chlorophyll and R-Phycoerythrin Content During the first four weeks, chlorophyll a levels all remained constant at approximately 0.O6mg-g-1 fresh weight of tissue (Fig. 3). Data from dark and pale thalli have been averaged in these figures unless otherwise noted. There were no significant differences, neither among nitrate treatments nor among weeks (ANÖVA, p».62). R-Phycoerythrin levels did change over the course of the experiment. Initially, the dark tissue had more pigments than the pale colored tissue (1.95 vs 1.41 mg/g fresh weight). However, concentrations in all thalli decreased, including those in the natural seawater (Fig 4). There were significant differences between the nitrate treatments as well as between the weeks (Pk.005). Samples harvested from the ocean at the end of the experiment had nearly identical phycobilin levels to those obtained initially (dark thalli had an average of 2.025 mg/g wt, and pale an average of 1.597 mg/g wt). Thus, there was no similar ocean trend, for either the pale or the dark thalli. Composition of Algal Tissue The percentage of carbon in the thalli gradually increased over the month of the experiment (Fig 5). ANOVA results indicated that there was a significant difference between weeks (Pk.05), but not between nitrate treatments. Samples taken from the ocean at the end of the experiment had similar percent composition to those taken at the start, for both carbon and nitrogen (24.36% carbon for dark and 22.99% for pale thalli; 2.955% nitrogen for dark and 2.805% for pale thalli). Levels of nitrogen in the thalli did not change significantly during the experiment, either between weeks or treatments (Fig. 6). However, when the pale tissue is examined separately, it is obvious that the thalli in the 20 uM NO3 treatment increased in percent nitrogen, while that in the 0 uM NO3 tanks hardly increased at all (Fig 7). Although this difference was not 10 statistically significant (p20.18), probably because sample sizes were limited, it is worth noting. Discussion Ambient nitrate levels and sufficient light affect the concentration of phycobilins in the thalli of Rhodymenia pacifica (Fig. 4). It is clear that, under reduced nitrate, their phycobilin concentration decreases. Those thalli which did not receive any nitrate at all had the lowest levels by the end of the experiment. This suggests that the bleaching in R. pacifica observed during El Ninnos is at least partly caused by breakdown of phycobilins in response to lowered ambient nitrate levels with sufficient light. Thalli which were pale at the beginning of the experiment demonstrated this the most. Due to their initial lower phycobilin levels, they must have been much more susceptible to decreased nitrate concentrations. The dramatic decrease in pigment levels suggests that they were being degraded very rapidly in the thalli to obtain the nitrogen for needed metabolic functions. However, why the thalli in 10 and 20 uM NÖ3 treatments had similar phycobilin concentrations throughout the experiment is unclear. Rhodymenia may absorb nitrate from the water at a faster rate than estimated; thus both treatments may have been nitrate stressed. Nitrate was added daily, and it is possible that the thalli absorbed it so quickly that after a few hours no nitrate was left in the water. Water samples taken twenty-four hours after nitrate was added were frozen and will be analyzed. Results from these samples will demonstrate if all the nitrate was absorbed each day or not. If Rhodymenia absorb nitrate faster than expected from the original nitrate calculations, this would explain the lowered phycobilin levels in all of the artificial seawater treatments. It is surprising, however, that even the thalli in natural seawater showed decreased phycobilin levels over time. Because all tissue samples that were weighed weekly remained constant or decreased in mass, the algae must have been under some degree of stress; although the tissue grows slowly, some increase in mass would have been expected. Stress was also obvious from the thalli which were turning green. This change in tissue was similar to the normal changes of nitrate deprivation; in the ocean thalli become blotched with green or yellow tissue, and in this experiment the tissue became green and disintegrated very easily. Green sections had, obviously, little or no detectable phycobilins. In the natural seawater tanks there was little green tissue; this suggests that the thalli were not stressed to the same degree as those in the artificial seawater. Possibilities include nitrate stress as well as the lack of another nutrient needed for algal growth, since green tissue appeared in much larger quantities in the artificial seawater tanks. However, there is no straightforward way to determine what exactly was different in the artificial seawater without further experimentation. The significant increase in percent carbon among weeks is consistent with algae which are nitrogen limited (Hanisak 1983). However, it is not known if the additional carbon was incorporated into carbohydrates or used for producing new structural tissue. When the measured growth rates are considered (Fig. 1), it becomes clear that the thalli were deteriorating, not growing. Thus, the increase in carbon was most likely incorporated into carbohydrates. All of these factors discussed demonstrate that, under sufficient light and limiting nitrate, phycobilin levels in Rhodymenia pacifica 1 will decrease. Thus, during an El Nino, at least part of the observed phycobilin decrease is due to these conditions. Acknowledgments I would like to thank my advisor, Jim Watanabe, for advice on my project throughout the quarter. Special thanks goes to the Monterey Bay Aquarium, in particular Roger Phillips, for his support as well as the use of his lab space, spectrophotometer, elemental analyzer. Deb Robertson’s insights on experimental design and pigment extraction were of great help to me. Stuart Thompson was kind enough to let me use his lab for the preparation of the artificial seawater. In conclusion, I am grateful to all those who went diving with me to collect the Rhodymenia. 13 Literature Cited Beer, S. & A. Eshel. 1985. Determining phycoerythrin and phycocyanin concentrations in aqueous crude extracts of red algae. Aust. J. Mar. Freshw. Res. 36, 785-792. Bold, H. & M. Wynne, 1978 Introduction to the Algae: Structure and Reproduction. Englewood Cliffs: Prentice-Hall, Inc. p. 450-452. Collier, J. & A. Grossman, 1992. Chlorosis induced by nutrient deprivation in Synechococcus sp. strain PCC 7942: Not all bleaching is the same. Journal of Bacteriology. 174 (14): 4718-4726. Gannt, E. Pigmentation and Photoacclimation. 1990. In,Biology of the Red Algae, eds. K. Cole & R. Sheath. pp. 203-219. Cambridge University Press. Hanisak, D. The Nitrogen Relationships of Marine Macroalgae. 1983. In, Nitrogen in the Marine Environment,, eds E.J. Carpenter & D.G. Capone pp. 699-730. Academic Press. Jeffrey & Humphrey. 1975. Biochem. Biophys. Phlanz. 167:191-194. Lobban, C, Chapman, D & B. Kremer. 1988. Experimental Phycology: A Laboratory Manual. pp. 127-128. New York: Cambridge University Press. Reed, R. Solute Accumulation and Ösmotic Adjustment. 1990. In,Biology of the Red Algae, eds. K. Cole & R. Sheath. pp. 203-219. Cambridge University Press. Vergara, J. 1993a. Effects of nitrate availability and irradiance on internal nitrogen constituents in Corallina elongata. Journal of Phycology. 29(3):285-293. Vergara, J., Niell, F. & M. Torres. 1993b. Culture of Gelidium sesquipedale (Clem.) Born. et Thur. chemostat system: Biomass production and metabolism responses affected by nitrogen flow. Journal of Applied Phycology. 5(4): 405-415. Figure Legends Figure 1: Weight of Samples of Rhodymenia pacifica Figure 2: Percent of Green Thalli in Different Nitrate Treatments Figure 3: Chlorophyll Levels in Rhodymenia pacifica Figure 4: R-Phycoerythrin Levels in Rhodymenia pacifica Figure 5: Percent Carbon in Rhodymenia pacifica Figure 6: Percent Nitrogen in Rhodymenia pacifica Figure 7: Percent Nitrogen in Paler Rhodymenia pacifica Figure 1 1 - — g Week 20uM NO3 — 1OUM NOS —n OuM NO3 —g seawater Figure 2 20 10 NO3 leve ae Pale 2 0 0 OE Source NO3 Week NO3 x Week Error Figure 3 0.08 0.06 - 0.04: 0.02 000 + Week Analysis of Variance Degrees of Mean-Square F-Ratio Freedom 0.00000947 0.608 0.00000161 0.103 0.198 0.00000308 24 0.00001557 0.616 0.902 0.947 E OuM NO3 E 1OUM NO3 20uM NO3 seawater Figure 4 5 82 EE A Week Analysis of Variance Degrees of Source Mean-Square Freedom NO3 0.376 Week 0.759 NO3 x Week 0.142 Error 0.064 32 Post-Hoc Tests Week 4: Natural seawater vs. 0 uM NÖ3 (p=.039) 0 uM NO3: Week 1 Week 2 Week 4 p=0.00 p=0.027 F-Ratio 5.879 11.583 2.223 0.003 0.000 0.047 Week 3 p=0.016 D OUM NO3 E 1OuM NO3 20uM NO3 seawater Source NO3 Week NO3 x Week Error Figure 5 Week Analysis of Variance Degrees of Mean-Square F-Ratio Freedom 0.780 0.932 4.762 3.987 1.110 1.326 1.194 24 0.517 0.032 0.385 E OUM NO3 E 1OuM NO3 20uM NO3 seawater Source NO3 Week NO3 x Week Error Figure 6 Week Analysis of Variance Degrees of Mean-Square F-Ratio Freedom 1.875 0.098 1.197 0.062 0.109 2.097 0.052 24 0.161 0.319 0.091 □ OUM NO3 E 1OUM NO3 20uM NO3 seawater Source NO3 Week NO3 x Week Error Figure 7 3.6 3.5 - 3.4 - 3.3 3.2 3.1 3.0 2.9+ 4 Week Analysis of Variance Degrees of Mean-Square F-Ratio Freedom 0.095 2.532 0.035 0.940 0.011 0.281 0.037 P 0.187 0.387 0.624 — — OUM NO3 — 20uM NO3