ADDITIONAL INFORMATION, IF ANY, CONCERNING AUTHORS, ADDRESS, TITLE, OR CITATION DATA PLEASE TYPE ABSTRACT DOUBLE SPACED BELOW BARIBAULT, WILLIAM H. (Hopkins Marine Station of Stanford University, Pacific Grove, California). Nitrogen Excretory Products in the Limpet Acmaea (Mollusca: Gastropoda: Prosobranchia). The Veliger Nitrogen excretory products were examined in the genus Acmaea by a microdiffusion technique for urea and ammonia and a colorimetric technique for uric acid. Five species were examined, varying in vertical distribution. Similar concen¬ trations of ammonia, urea, and uric acid were found in all five species. A large amount of intraspecific varition in the distribution of these compounds was noted, especially in the high intertidal forms Acmaea scabra and Acmaea digitalis. These variations might reflect individual differences in enzyme activity, individual differences in diet, or adaptive responses to the environment. E PLEASE DO NOT TYPE BELOW THIS LINE 4 c Nitrogen Excretory Products In The Limpet Acmaea (Mollusca: Gastropoda: Prosobranchia) by William H. Baribault Hopkins Marine Station Stanford University. Pacific Grove, California X Footnott William H. Baribault NTRODUCTION Examination of excretory products in the molluscs indicates that more terrestial forms tend to be urico¬ telic and aquatic forms tend to be ammonotelic. This is especially evident in Needham's classic study of the littorinid snails where an ascending order of uric acid production was found to be directly correlated with increasing height in the intertidal zone (Needham, 1935). als In this regard, members of the genus Acmaea present an interesting contiuum. On the Monterey Peninsula, populations of the five common species of this genus are found varying from +0.0 feet to +5.0 feet. To see if any correlations could be found between intertidal zona¬ tion and nitrogen excretory patterns, a comparative analysis of excretory products in this genus was made. METHODS AND MATERIALS The five species of Acmaea used in this investi¬ gation were Acmaea digitalis Eschscholtz, 1833; A, lima¬ tula Carpenter, 1844; A: scutum Eschscholtz, 1833; ap shs 823 and A. scabra (Gould, 1846). All species were collected from the intertidal area at periods of low tide on Pescadero Point in Monterey County, California. The same collection procedure was followed for all animals studied. Each animal was removed from the rock William H. Baribault substratum, with care to avoid loss of fluid from the mantle cavity, and placed into a capped glass vial containing 5 ml of artificial sea water (Harvey, 1954). The animals were kept in the vials at sea water tempera¬ ture for two to three hours. The artificial sea water (ASW) was decanted into a graduated centrifuge tube, the limpet removed, and each vial rinsed with 2 ml of ASW. Each animal was then gently squeezed, anterior end down over the centrifuge tube, to empty the mantle cavity of any remaining fluid. The pooled fluid was brought to 10 ml with ASW, centrifuged to remove any particulate matter, and the supernatant decanted and frozen until used for analyses. Total nitrogen, ammonia nitrogen, and urea nitrogen were assayed by the microdiffusion method of Ternberg (1965). The total nitrogen was determined on a 1 ml sample after wet ashing with 1 ml of sulfuric acid saturated with cop¬ per sulfate. Ashed samples were diluted with 5 ml of distilled water, and 4 ml of 10 N sodium hydroxide were substituted for the sodium carbonate solution used in Ternberg's original method. Urea was determined as ammonia after a thirty minute incubation with 0.1 ml of a 50 mg/ml solution of urease (obtained from Matheson, Colman, and Bell) in distilled water. Uric acid was determined colorimetrically by the method of Sobrinho-Simões (1965). Prior removal of proteins was found to be unnecessary. William H. Baribault Gaseous excretion of ammonia was determined by pla¬ cing the intact animal into a dry diffusion apparatus for 24 hours. Gaseous ammonia was collected by absorp¬ tion on alkaline filter paper, and analyzed for ammonia by Ternberg's procedure. The microdiffusion assay procedure was calibrated with ammonium sulfate solutions of known concentrations and found to be extremely reproducible (Figure 1) with triplicate and duplicate determinations on the same sample revealing small standard deviations (eg., Acmaea scutum NH, - N, 7.0 + 0.25 ug). RESULTS Ammonia, urea, and uric acid were found to be ex¬ cretion products in all species of Acmaea investigated. Some species showed wider individual varations in amounts of certain excretory products than other species. For example, the values for ammonia nitrogen in Acmaea digitalis ranged from 0.4 to 25 ug N, whereas for Acmaea scutum the range was much less, varying from 6 to 10 ug N (Table 1). In terms of individual varation, the greatest variability in ammonia nitrogen was found in A. digitalis, followed by A. scabra, A. pelta, A. limatula, and A. scutum. Variation in uric acid was greatest in A. pelta, followed by A. scabra, A. limatula, A. scutum, and A. digitalis. William H. Baribault The percentage distribution of the various nitro¬ genous compounds, based upon mean values, is shown in Table 2. The comparison between the five species indicates that relatively more ammonia is excreted by Acmaea dig¬ italis and A. scabra, that less uric acid is excreted by A. digitalis, and that A. scabra and A. scutum excrete less urea. It can also be seen that greater than 80% of the total nonprotein nitrogen can be accounted for by these methods. Gaseous ammonia was found to be excreted in the five species of Acmaea examined with the dry diffusion tech¬ nique described above. Those forms found higher in the intertidal zone, A. scabra and A digitalis, produced more of the gaseous product than the lower intertidal forms, A. scutum, A. limatula, and A pelta. The mean value after 24 hours was 2.9 ug NH,-N for the higher species and 2.0 ug NH-N for the lower ones. DISCUSSION The microdiffusion and colorimetric techniques, coupled with the collection procedure, haveprovided a means of analysis of individual specimens of the genus Acmaea. The extreme standard deviations obtained (eg., in A. digitalis, NH,-N 8.9 + 8.3 ug) indicate very large individual differences. The deviations did not result from the assay procedure, which, as previously indicated, 6 William H. Baribault TABLE CAPTION TABLE I Relative ug nitrogen excretory products with standard deviations for eight animals for each species. Rest nitrogen is the difference between the total nitrogen and the sum of the three pro¬ ducts. TABLE II Percentage excretory products calculated rom mean values of table I. 50 O 1.0 0.9 O.8 ).7 0.6 O.4 O.3 0.2 - O.1 kakaaka- 1 2 3 4 5 6 U9 NH3 N William H. Baribault Figne NH3 N Urea N Uric Acid N Rest N Total N William H. Baribault NITROGENOUS EXCRETORY PRODUCTS IN ACMAEA Acmaea Acmaea Acmaea Acmaea Acmaea scabra limatula digitalis scutum pelta 10.6 + 6.3 8.9 + 8.3 8.5 + 3.9 7.5 + 1.8 9.25 + 4.6 3.75 + 3.2 5.9 + 4.2 7.3 + 5.2 6 f1.5 11.1 + 4.2 14.6 + 4.9 14.7 + 4.3 7.9 + 1.7 13.3 + 2.9 17,8 + 6.7 5.0 + 3.5 5.0 + 2.9 2.8 + 2.7 .7 1 4.2 5.75 + 4.7 33.0 + 7.9 27.8 + 7.1 83.3 1 8.2 82.0 + 7.3 43.9 + 9.1 able S. NH3 N Urea N Uric Acid N Rest N Total N William H. Baribault RIBUTION OF NITROGEN PRODUCTS PERCENTAGE DI Acmaea Acmaea Acmaea Acmaea Acmaea Pelta digitalis limatula scutum scabra 21 32 25.5 23.5 32 25.5 22 14.5 11.4 21 40.5 44.5 44.5 42.5 28.5 13 12 19.5 18.5 100 100 100 100 100 ae illiam H. Baribault CAPTIONS FIGURE I Calibration of diffusion apparatus with ammo- nium sulfate solutions using optical density as a measure of ug concentration. TABLE I Relative ug nitrogen excretory products with standard deviations for eight animals for each species. Rest nitrogen is the difference between the total nitrogen and the sum of the three pro¬ ducts. TABLE II Percentage excretory products calculated from mean values of table I. William H. Baribault highl was reproducible. These maximal and minimal components of variability, only seen in comparing indi¬ viduals, would be masked by methods that measure pooled mara . In particular, these results demonstrate the value of individual analysis. Although average values can be obtained, as in Table 2, the interspecific differences observed might therefore be misleading. Several hypothses can be advanced to explain the large individual variation in the relative amounts of excretory nitrogen. One is that enzyme content varies within the population, resulting in different distri¬ butions of excretory nitrogen products when comparing individuals. This is especially suggested by William's work on biochemical variation within individuals of the same species (Williams, 1966). Another explanation is that individual variations in the diet would result in the observed distribution of nitrogen products. A third possibility is that the limpet changes its major products of nitrogen excretion as a result of exposure to air during the tidal cycle. This is suggested by Needham's (1935) proposal that more terrestial animals tend to excrete uric acid, whereas more aquatic forms tend to excrete ammonia. This hypothesis is also sugges¬ ted by the larger variations in the higher forms, which would have been exposed to longer, and more variable, periods of dryness. If correct, this could suggest a S. William H. Baribault unique adaptation of the higher forms to secrete more uric acid when dry than when wet. Such a transition would be of adaptive value, since ammonia and urea at high concentrations are toxic. Although urea was found to be excreted by all species examined, the metabolic mechanism of its formation is not clear. Campbell (1966) found no arginase in the spP digestive gland of an Acmaea, suggesting the absence of the ornithine cycle in this species. However, Campbell only examined the digestive gland, leaving open the pos¬ sibility that the enzyme might be present in other tissues. While his results possibly eliminate the ornithine cycle, other pathways based upon purine degradation could be alternative mechanisms for urea production. For example, in fishes, products of purine breakdown from uric acid give rise to urea via the enzyme allantoicase (Laskowski, 1951). This pathway is also suggested by hi preliminary experiments indicating formation of urea by minced digestive gland in an ASW- uric acid solution. The finding that all three products are present, and the reported absence of arginase, suggests the pos¬ sibility that the source of ammonia nitrogen is by protein catabolism, whereas the urea and uric acid pro¬ ducts might result from purine catabolism. The nature of the nitrogen is not 5 William H. Baribault clear. Qualitative tests with 0.25% ninhydrin solution show the presence of peptides and amino acids in the samples obtained from the limpets. This may account for some of the 13-18% unidentified nitrogen. SUMMARY Nitrogen excretory products were examined in the genus Acmaea by a microdiffusion technique for urea and' ammonia and a colorimetric technique for uric acid. Five species were examinéd, varying in vertical distribution. Similar concentrations of ammonia, urea, and uric acid were found in all five species. A large amount of intraspecific variation in the distribution of these compounds was noted, especially in the high intertidal forms Acmaea scabra and Acmaea digitalis. These variations might reflect individual differences in enzyme activity, individual differences in diet, or adaptive responses to the environment. William H. Baribault ACKNOWLEDGEMENTS I am indebted to Dr. John Phillips for his advice and encouragement during this investigation, Appreciation is extended to Dr. David Epel for his helpful recommendations in the preparation of the manuscript. The work was made possible by Grant GY 806 from the Undergraduate Research Participa¬ tion Program of the National Science Foundation. William H. Baribault LITERATURE CITED CAMPBELL, J. W. Distribution of arginase activity in molluscs. 1966. Comparative Biochemistry and Physiology. 17: 259-270 HARVEY, H. W. 1954. Chemistry and fertility of sea waters. Cambridge University Press LASKOWSKI, The Enzymes, Chapter 27, ed. Sumner and Myrbäck, 1951. Academic Press, New York NEEDHAM, J. 1935. Problems of nitrogen catabolism in invertebrates. Correlations between uricotelic metabolism and habitat in the phylum Mollusca. Biochemical Journal 29: 238-251 HO-SIMOES, M. SOBRIN A sensitive method for the measurement of serum 1965. uric acid using hydroxylamine. Journal of Laboratory and Clinical Medicine 65: 665-668 IRNBERG, J. L. 1965. Colorimetric determination of blood ammonia. Jour¬ nal of Laboratory and Clinical Medicine 56: 766-776 WILLIAMS, R. J. Individuality in nutrition: Effects of Vitamin A¬ 1966. Deficient and other deficient diets on experimental animals. Proceedings of the National Academy of Science 55: 126-134 59 William H. Baribault FOOTNOTES Page 1-Permanent Address: 60 William H. Baribault FIGURE CAPTIONS FIGURE I Calibration of diffusion apparatus with ammo- nium sulfate solutions using optical density as a measure of ug concentration. c