AN ANALYSIS OF NITROGEN WASTE PRODUCTS IN LORINA PLANAXIS Ann Louise Cox May 30, 1964 Biology 175h Few studies have been made of the nitrogen waste products of the littorines. Spitzer in 1937 (see Fretter and Graham, 1962) studied the nitrogenous excretory products of Littorina littorea, a gastropod located in the low intertidal of Europe. Needham (1935) studied the uric acid content of four species of littorines, but did not analyze the kidney for other waste products. The purpose of this investigation, therefore, was to obtain data on the total non-protein nitrogen, NPN, and the various nitrogenous constituents of the kidney of Littorina planaxis, a gastropod with wide vertical distribution in the intertidal of California. These earlier studies note that excretory products are a function of the environment but fail to take into account the fact that this gastropod is subjected to a wide daily variation in water availability which could cause variation in the kidney contents. In the present study attention was paid to the variation in the tidal cycle and its possible effect on the nitrogenous consti¬ tuents of the kidney. METHOD Two areaswere chosen from which to collect snails: one population was located at the lower limits of the species in the intertidal where there is water present 90% of the time: The snails here measured from 7-9 mmin size. The second population occurred at the upper limits of the intertidal where the snails are exposed to air, wind, desiccation, and such approximately 95% of the time and range in size from 10-12 mm. Collections were made at various periods through five tidal cycles. Two series of observations two and one-half weeks apart were carried out on small numbers of snails from both areas. The second, less complete, was intended as a check on the first. Five samples of ten snails each were examined at each point in the tidal cycle in an effort to obtain an accurate estimation of the concentration range of these products. At each of eight different times in the tidal cycle fifty snails were gathered from one area and the kidneys dissected out immediately. The dissections were trouble- some, because kidney tissue is intermingled with surrounding body tissue and difficult to extract whole. Ten kidneys were weighed together after all excess water had been removed. This tissue was ground and deproteinized with dilute sulfuric acid and sodium tungstate at ph 6-7. There resulted five protein¬ free filtrates from each point in the cycle. The total NPN was determined by the Kjeldahl method of digestion with acid followed by Nesslerization. Ammonia content was also determined by Nesslerization, as was urea, after hydrolysis with urease (Baker and Adamson). Uric acid was determined by the method of Benedict and Franke (1922). All colorimetric measurements were made with a Klett-Summerson Photoelectric Colorimeter and converted to milligrams of nitrogen with a standard curve prepared on the same machine. RESULTS It can be observed from Figure 1, which shows the variation in the nitrogenous excretory products of snails in the low intertidal, that there is a definite drop in NPN at Low Low Water when the snails were receiving a minimal amount of wave action. (Hereafter, all tides will be referred to with the appropriate capitals, eg. LLW) Another low point occurred at mid-HHW-HLW D when the water was receding. The largest amount of NPN (3.45-5.58 mg NPN/ gm. kidney) in the kidney of snails found at this level was at HLW with a secondary peak at mid-LLW-HHW. Because no reading was taken at mid-HLW-LHW, it is inaccurate to state unequivocally that HLW was a definite high point with a gradual decline thereafter. Figure 2 showing the various nitrogenous excretory products through a second tidal cycle, suggests that, on the contrary, there was a peak reached at mid-HLW-LHW. Again, in Figure 1 ammonia seemed to vary directly with the total NPN at each point in the tide, with the one ex¬ ception of HHW when ammonia content fell but NPN did not. During this period snails were being submerged once every 30 seconds and splashed continuously. The urea content curve was approximately the same as that of ammonia, but urea usually seemed to be in smaller quantities. However, at LLW there was more urea, 12-427 of NPN, than ammonia, 9-197, and quite a lot of undeter¬ mined nitrogen, 46.47-77.122. Uric acid seemed to be present in only trace amounts. (Refer to Table 1) Observations made in the second tidal cycle, taken two and one-half weeks later, on low L. planaxis, show that the least amount of NPN occurred again at LLW (See Figure 2). Here there was only one measurement, but it is significantly lower than any point on either side. There was also a decrease at HLW, but none at mid-HHW-HLW as in the first series of test. As for the constituents, ammonia seemed to follow the same curve as that in the first cycle, with low points at LHW, LLW, and HHW. Urea again showed the same correspondence with ammonia except at LLW when it constituted 46.77 of NPN and ammonia 40.5%. In this O- DADN series of tests, more urea was present (average,25.47) than in the first tidal cycle (average 22.137). The ammonia-N content was also increased from 33.34% to 41.7%. Here, as in the first run, uric acid was present in only trace amounts, except at irregular times, at LLW, when it amounted to as much as 3.13%. Generally those snails from higher in the intertidal showed a greater variation in total NPN at any one time in a tidal cycle than the lower snails tested simultaneously. From Figure 3 it can be observed that snails in higher areas did not show the low NPN at LLW that snails from lower areas did. On the contrary, NPN was at its lowest at HHW and immediately after LHW, the only periods in the cycle when these snails received water directly in the form of splash. At LHW a wide range of NPN was seen, 2.83-6.36 mg/ gm. of kidney. This could be the result of the lower snails collected having been splashed but the higher ones remaining dry. Ammonia did not show quite the same correspondence with NPN as it did in the lower areas. There seemed to be less drastic decreases. The most noticeable one occurred at mid-LHW-LLW. This corresponded to the drop in NPN evidenced at the same time. There was a rise after HHW and also a peak at LLW. Overall, the percentage of ammonia-N in NPN was less, 24.927, and showed less variation than that of ammonia-N found in snails in lower in the intertidal (33.34%) Urea, as in the lower areas, corresponded to the ammonia, always remaining less and falling quite a bit at HHW. Again uric acid was found in negligible amounts. The second series of testin the high area involved only a small part of the tidal cycle, so little can be said about the total picture. Two interesting observations can be made, O O HETTHNTE e however: uric acid appeared in large quantities fro the first time in the course of this investigation; up to 20.97 of the NPN at mid-LHW-LLW consisted of this waste product. Simultaneous with this sudden increase in uric acid, urea and ammonia decreased and subsequently rose again when uric acid nitrogen fell. DISCUSSION In general it can be stated that there was variation in NPN as well as constituent products in the kidney of Littorina planaxis within a tidal cycle. Needham's assumption, an important basis for his analysis, that the kidney retains the renal waste products for very long periods did not seem to hold for the snails studied here. More specifically, kidneys of snails located at the lower limits of the species' distribution showed an interesting anomaly at LLW. One might have expected a greater amount of NPN at that time than others,because there was no water available for diffusion of urea and ammonia into the environment; however, the contrary was seen to occur. The amount of ammonia-N averaged 2.25 mg/gm of kidney at this time, whereas an average of all the other measurements was 3.54 mg/gm of kidney. If this is correlated with the fact that the ammonia-N percentage at LLW, 9-197, was very much lower than that normally found, 33.34%, it might be hypothesized that ammonia is being eliminated as a gas. Or, because ammonia is toxic and requires much water for elimination, perhaps less ammonia is produced by the snail at this time in the tidal cycle. At any rate, all snails tested seemed to be exhibitig the same tendency toward very low NPN and ammonia at this time. Not including the LLN percentages, it would seem that the average percentage of ammonia-N, 33.34%, in this littorine corresponds to the 39.9% given by Spitzer (1937) for L.littorea, a snail occurring lower in the intertidal. Only three ammonia measurements were over Spitzer's maximum of 50%. Concerning the other constituents of NPN in the low areas, it seems that less urea than ammonia was found in the kidneys, except at LLW. This latter observation could be a result of the fact that urea had no way of leaving as a gas (as ammonia might), so it contiued to be stored in the kidney until enough water was available for elimination by diffusion. The average, as compared to Sptizer's figure of 12.6% was 22.13%. This increased slightly to 25.4% in the second tidal cycle. As for the very low uric acid content in the snails low in the intertidal, it might be argued that since these L. plandis are around water 90% of the time, they have no need of utilizing a water con- servation mechanism; the uric acid present might merely represent the degradation of nucleic acids. However, the second series of analyses showed slightly greater amounts of uric acid being produced at irregular intervals. This at least indicates a capability of synthesizing uric acid from ammonia. Snails from the upper extremes in the intertidal also showed variation in kidney contents with tidal changes. These results seem to be more easily explained: urea and ammonia diffuse into the water when it is available to the snail, at LHW and HHW; in the interim, there is storage of the products and gradual increase, with one drop at HL, which is perhaps due to ammonia gas elimination. It would appear that there was more NPN/gm of kidney in snails from the higher location than in those found lower. It is possible that a certain minimal amount of waste is continually diffusing into the water available to the lower snail, but those in the higher regions have no water for this elimination. This difference in NPN might also be due to the ease of obtaining kidney free of other tissues in the larger snails from the high area. This separation is more difficult in the smaller snails from lower in the intertidal. This other tissue contains no NPN but contributes to the weight of the sample. Along with the greater amounts of NPN there seemed to be less ammonia-N (24.927) in snails from the higher areas. Perhaps, because ammonia is more toxic than other waste products and re¬ quires more water for excretion, a snail exposed to air for 957 of the time can't tolerate such high percentages of ammonia as snails in the lower, wetter areas (33.347). The one time,LLW, when the lower snail was exposed to an environment similar to that of the higher snails there was a remarkable decrease in ammonia-N. A large percentage of undetermined -N was found in the first series of tests, 63.587, and much less two and one-half weeks later, 45.76%. This same decrease in undetermined-N was found in snails from the lower regions, with 46.717 in the first cycle and 31.06% in the second. Perhaps, this observation could be correlated with the finding that urea was in much smaller quantities in the first run, 11.07%, than in the second,21.87. When added together, ureatundetermined-N =- 74.65% NPN in the first series and 67.56% in the second. These percentages seem to be very similar. The "equation" does not hold for snails in the lower regions. Perhaps, a change has taken place in the system of the snail with the onset of the summer tides, warmer weather, and more nutrient growth. This suggestion implies that urea and undetermined-N are products, either terminal or intermediate, of the same pathway. Further investigations to determine what these unknown materials are, as well as studies of this correlation with urea, could prove interesting. Such analyses might reveal the pathway by which urea is formed. In the second abbreviated series of tests on snails from high in the intertidal, uric acid was found to be in vast quantities at irregular intervals in the tidal cycle. With each increase in uric acid there was a simultaneous decrease in urea, and vice versa. Although urea varied at other times when only trace amounts of uric acid were found, this inverse relationship might prove interesting for further study. Perhaps uric acid and urea are a part of the same metabolic pathway. The problem of uric acid production is an interesting one. Needham (1935), in proof of his hypothesis that limited access to water results in an increase in the formation of uric acid, presents definite ranges of concentrations of uric acid for the four species he tested. Littorina rudis is located a little below L. planaxis in the intertidal and it contained 5.1 mg uric acid/ gram dry kidney weight. If the data obtained in the present study is calculated in the above manner, the largest figure for L. planaxis is 3.5 mg uric acid/ gm wet kidney weight; this large amount was found in L. planaxis only once in the tidal cycle, with smaller amounts occurring at other times but only sporadically. Certainly these quantities were not constant, in contrast to Needham's findings. It is suggested, therefore, that L. planaxis has no prolonged increase or retention of uric acid but that production is spasmodic and elimination rapid. Ideally, the analyses of the kidney contents of L. planaxis should have been carried on through one day's tidal cycle. Also, an examination of the food eaten by the snails of these two extreme areas in the intertidal might, to some extent, explain the differences in the amounts of the various nitrogenous excretory products found between the low and high snails in this investigation. SUMMARY 1. There was found to variation in the total NPN as well as constituent products in the kidney of Littorina planaxis. 2. Snails from low in the intertidal contained more NPN, ammonia, and urea than those in the high regions. 3. Snails in the low area contained very little MPN and ammonia at LLW. 4. Urea was found in smaller quantities than ammonia in snals from both regions; in both areas, however, the average amount of urea increased from the first tidal cycle observation to the second, carried out two and one-half weeks later. 5. There was less undetermined-N in the kidneys of low area snails than high. These averages decreased over a period of two and one-half weeks. 6. Uric acid-N was negligible until the second tidal cycle observations, where it then constitued up to 20.77 NPN in the kidneys of higher snails and 3.137 NPN in those lower. This production was very spasmodic with rapid elimination. 58 BIBLIOGRAPHY BALDWIN, ERNEST. Dynamic Aspects of Biochemistry. Cambridge University Press, (1957.) CARTER, "Intertidal Exposure of the Littorine's." Jour. Mar. Biol. Assn. 18: 435. (1931) FOLIN, OTTO. "Standardized Methods for the Determination of Uric Acid in Unlaked Blood and in Urine."(1933); Jour. of Biol. Chem. 101: 11. LEVINSON, S. AND MAO FATE, R. Clinical Laboratory Diagnosis. Lea and Fibiger, Philadelphia. (1951) NEEDHAM, J. "Uricotelism and Habitat of Gastropods" Biochem. Jour. 29: 238-251 (1935). NEEDHAM, J. "Nitrogen excretion, Snails, as an example of reversibility in Evolution" Biol. Rev. 13: 224-251 (1938) J.A. COLIN. The Biology of Marine Animals Interscience NICOL, Publishers, Inc. N.Y. PETERS, J.P. AND VAN SLYKE, D.D. Quantitative Clinical Chemistry Baltimore, Williams and Wilkins, Vol. 1; Biochemical Interpretations. (1946) PICKEN, L.E.R. "The Mechanism of Urine Formation in Invertebrates" J. Exp. Biol. 13: 309. (1936) PROSSER, C.L. (ed). Comparative Animal Physiology. London, Saunders, 1950. TODD AND SANFORD. Clinical Diagnosis by Laboratory Method. Philadelphia and London; Saunders. FRETTER, VERA AND GRAHAM, ALASTAIR, British Prosobranch Molluscs: Their Functional Anatomy and Ecology. Ray Society, 1962 BENEDICT, S.R. AND RANKE, ELIZABETH. "A Method for the Direct Determination of uric acid in Urine." J. Biol. Chem. 52: 387-391. June (1922). TIDE HLW mID LAW mID LLW mID HHW m1D HLW mID LHW m1D LLW MID H HW m1D HLU mID LHW m1D LLW mID HHW LAW miD RID LEW HHW-LLO Von- Peors Mreocee Perrn URIC ACID OTHEES m6. NPN NA, UREA 6M. KIDNEY % N % N % N % N 1/90 - 575 1, 1ou Besa 3.45-5.58 0.382-0.599 46.85- 63.56 1.85- 16.05 26.3- 43.3 NO - DATA 0.276- 1.02 45.5 - 65.48 6.56 - 13.6 2.73 - 4.16 19. 9 - 43.4 0.262- 1.02 63.49-90.24 2.35 - 3.87 9.57- 35.5 1.25 -4.16 12.4 - 41.6 46.4 -77.12 0.233- 1.07 9.25 - 18.0 2.92 -4.35 30.26 - 45.5 11.94 - 42.4 O.262-0.182 26.5 -48.16 O.343-0.866 31.2 -64.7 2.57 -3.8 13.0 -40.8 9.6 - 33. 0.336-0.770 14.8 -47.75 2.15 - 3.1 15.5 - 56.7 8.75 - 44.7 5119 1A. LouRee 5 122 5.6 - 7.2 40.0 55.0-65.2 0.322 4.68 43.0 -73.8 21.5 -43.2 O. 300-0.533 1.4 -31.8 6.68 - 8.42 5.24-8.0 26.2 -35.5 1.61 - 1.97 19.2 -24.5 38.39-52.63 20.3 - 25.6 0.705-0.800 17. 3-36.2 37.5-61.6 6.77 -6.9 40.5 4.31 46.7 3.13 9.67 o.61 -1.68 13.4 - 47.3 5.98-6.7 27.3-30.3 24. (2-21.8 o.168-1.76 7.01 - 8.55 20.0-37.0 8.75-13. 52.63-71.88 30.18 1.43 59. 64 8.33 8.75 4130 515 Hen Ress 2. 3.13-4.46 5.3 -16.55 59.75-68.67 14.65-34.7 0128 -0.172 4.89- 6.44 70.18-79.70 6.68-12.35 0.121 - 0.334 7.61 -21.7 o.181 - 0.275 2.83-6.36 15.95-35.4 4.0 - 25.6 38.72 -74.70 2.44-9.13 7.58 -27.8 O.150-0.280 45.48-68.81 17.9 -26.5 6.6 - 25. 23.7- 49.8 O.141 -0.332 3.51 - 5.65 25.77-69.86 O.108 -0.156 5.01 -7.49 13.8 -22.8 2.09-13.9 69.56 -76.49 2.31 -4.02 21.4-61.0 0.150 -0.42 4.06 - 9.95 33.70 -70.8 2-h Hieneea 5119 - 5 122 17.0- 32.2 12.8 -15.2 18.3 - 38.9 5.53-7.53 36.7-38.9 28.5-29.8 15.9 - 29.3 O.409-0.608 40.49 -55.0 10.45 -11.5 6.04 - 9.51 11.0-22.4 0.823-20.9 24.5-37.8 30.3 - 52.3 O.113-0.135 22.1 -25.0 49.0 - 55.82 28.8-29.05 8.25 -9.6 21.6 - 73.62 0.127-0.213 3.9-8.85 17.5-45.8 8.75-32.4