- American Society of Limnology and Oceanography
Transcription
- American Society of Limnology and Oceanography
Notes in Daphnia: An improved two-compartment model and experimental test. Arch. Hydrobiol. 100: l20. LEHNINGER, A. L. 1970. Biochemistry. Worth. LI, W. K. W., H. E. GLOVER, AND I. MORRIS. 1980. Physiology of carbon assimilation by Oscillatoria thiebautii in the Caribbean Sea. Limnol. Oceanogr. 25: 447-456. MANAHAN, D. T. 1983. The uptake of dissolved amino acids by bivalve larvae. Biol. Bull. 164: 236250. MORRIS, I. 1980. Paths of carbon assimilation in marine phytoplankton, p. 139-l 60. In Primary productivity in the sea. Brookhaven Symp. Biol. 3 1. Plenum. PEIRSON, W. M. 1983. Utilization of eight algal species by the bay scallop, Argopecten irradians concentricus (Say). J. Exp. Mar. Biol. Ecol. 68: l-l 1. RASHEVSKY, N. 1959. Some remarks on the mathematical theory of nutrition of fishes. Bull. Math. Biophys. 21: 16 l-l 83. RAYMONT, J. E. G., R. T. STRINIVASAGAM, AND J. K. B. RAYMONT. 1969. Biochemical studies on marine zooplankton. 7. Observations on certain deepsea zooplankton. Int. Rev. Gesamten Hydrobiol. 54: 357-365. RIVKIN, R. B. 1989. Influence of irradiance and spectral quality on the carbon metabolism of phytoplankton. 1. Photosynthesis, chemical composi- Lmnol. Oceanogr., 36(4), 199 1, 807-8 14 0 199 1, by the American Society of Limnology and Oceanography, 807 tion and growth. Mar. Ecol. Prog. Ser. 55: 291304. ROBERTS, R. B., D. B. COWIE, P. H. ABELSON, E. T. BOLTON, AND R. J. BRII-TEN. 1955. Studies on the biosynthesis in Escherichia coli. Publ. Carnegie Inst. 607. 521 p. ROMAN, M. R. 1984. Utilization of detritus by the copepod Acartia tonsa. Limnol. Oceanogr. 29: 949959. SMITH, R. E. H., AND R. J. GEIDER. 1985. Kinetics of intracellular carbon allocation in a marine diatom. J. Exp. Mar. Biol. Ecol. 93: 19 l-210. SMITH, S. L., AND B. K. HALL. 1980. Transfer of radioactive carbon within the copepod Remora longicornis. Mar. Biol. 55: 277-286. SMUCKER, R. A., AND R. DAWSON. 1986. Products of photosynthesis by marine phytoplankton: Chitin in TCA “protein” precipitates. J. Exp. Mar. Biol. Ecol. 104: 143-152. TENORE, K. R., AND L. GUIDI. 1984. Carbon-14 net incorporation does not accurately estimate the weight-specific growth rate of the polychaete Capitella capitata. Mar. Biol. 79: 101-107. WALNE, P. R. 1973. Growth rates and nitrogen and carbohydrate contents of juvenile clams, Saxidomus giganteus, fed three species of algae. J. Fish. Res. Bd. Can. 30: 1825-l 830. Submitted: 27 June 1989 Accepted: 6 November 1990 Revised: 14 January 1991 Inc. Carbon, nitrogen, and phosphorus content of freshwater zooplankton Abstract-The amounts of C, N, and P in relation to dry weight were measured in natural populations of crustacean zooplankton from a humic lake. The elemental composition within a given species showed little seasonal variation, and experimental starvation or feeding did not cause any significant changes in the P content. C constituted 48+ 1% of dry weight with only minor variation among species. The mean C: N: P atomic ratios reflected large interspecific differences in P and N content and ranged from 2 12 : 39: 1 in Acanthodiaptomus denticornis to 85 : 14 : 1 in Daphnia longispina. Comparisons with Acknowledgments This work was financed by the research program on eutrophication of inland waters, supported by the Royal Norwegian Council for Scientific and Industrial Research. We thank Anne Lyche and two anonymous reviewers for comments on earlier drafts of this paper. published measurements indicate that this pattern is quite general and probably constitutional. These findings suggest that the species composition of the zooplankton community can have strong influence on the N : P ratio of recycled nutrients and thereby affect resource competition between phytoplankton species. Herbivorous zooplankton influence the proliferation of planktonic algae and bacteria through the simultaneous effects of grazing and nutrient recycling. As pointed out by Sterner (1989), zooplankton act not only as predators in a classical sense, but also have an indirect effect on resource competition between algal species and bacteria. The major forms of dissolved P and N released from zooplankton are easily accessible to phytoplankton and may be a major 808 Notes nutrient supply to the primary producers at certain times (Peters and Rigler 1973; Lehman 1980, 1984). Olsen and 0stgaard (1985) proposed a model wherein nutrient recycling was given implicitly by the balance between ingestion and utilization into somatic growth and reproduction. In a following paper, Olsen et al. (1986) supported this concept with results from field experiments, showing a strong dependence of the P release rate of Daphnia on the P : C ratio of the food particles. Sterner (1989) extended these ideas to a conceptual model in which grazers ingest food with highly variable C : N : P ratios while assimilating a relatively constant C : N : P ratio, releasing the difference between the two. This inference is in accord with the observation of Lehman (1984) that the egested portion of ingested food is generally more variable than the assimilated portion. Under these assumptions the zooplankton would drain a constant C : N : P proportion from food particles, resulting in a progressively diverging N : P ratio in the recycled nutrients which would be expected to have a strong influence on the competition between phytoplankton species (e.g. Kilham and Kilham 1984). Sterner (1989), admitting the lack of relevant data from freshwater localities, based the assumption of constant zooplankton C: N: P ratios mainly on extrapolations from the marine literature which indicates that N content is less variable in marine zooplankton than in phytoplankton. We here present measurements of C, N, and P content in six species of freshwater zooplankton- both in the field and under experimental conditions-as part of an integrated study of the zooplankton community in Kjelsasputten, a small, acid, brown-water seepage lake located in a forest area near Oslo. During the period of investigation, particulate C averaged 0.43 mg C liter-’ (Fig. I), with detritus probably making up 7590% (Hessen et al. 1990). Concentrations of particulate P and N were low, with the seston P : C ratio more variable than the N : C ratio (Fig. 1). The zooplankton community was dominated by the cladocerans Daphnia longispina, Holopedium gibberum, Diapha- 9 0 1.6 :, 1.2 E h’ 0.6 F 0.4 I May -8 Jun JUI Aw Sep act Fig. 1. Seasonal variation in seston composition in Kjelshputten, 1986 [pooled samples from epilimnion (O-3 m); see Hessen 19891. Lower panel-particulate C; middle panel-N : C ratio (by wt); upper panel P: C ratio (by wt). nosoma brachyurum, and Bosmina longispina and the Calanoid copepods Acanthodiaptomus denticornis and Heterocope saliens; rotifers and cyclopoid copepods made up < 5% of the zooplankton biomass. Further details on C cycling, community structure, and seasonal succession can be found elsewhere (Hessen 1989; Hessen et al. 1990). Field samples of zooplankton were taken by vertical (45-pm mesh size) net hauls at about biweekly intervals throughout the growing season from May to November 1986. Live animals were brought in lake water to the laboratory, collected on nylon screens, and immediately frozen (- 20°C). Before analysis, frozen animals were directly sorted by species and developmental stage while they thawed under a dissecting microscope. Care was taken to pick animals immediately upon thawing to prevent leakage of body fluids. Each sample consisted of 3-30 adults of similar size, giving an average sample size (rt 1 SD) of 157 + 8 5 pg dry weight (DW). Three parallel laboratory experiments were performed in a 17°C constant temperature room under an artificial 12 : 12 L/D Notes cycle. In each experiment a mixture of 2050 adults of D. longispina, H. gibberum, and B. longispina were added to 5 liters of water. The receiving natural lake water was given the following treatments: food removal (filtration through Whatman GF/F glass-fiber filters), inorganic P enrichment (addition of 10 pg Pod-P liter-‘), and food enrichment (addition of exponentially growing algae and bacteria). At the end of the experiment, the animals were harvested and 2-4 replicates analyzed for dry weight and P content after the same analytical procedure as the field samples, except that animals were processed live after anesthesia with carbonated water. The starvation experiment was terminated after 4 d when mortality increased rapidly, and the other two experiments were terminated after 2 weeks. Tests with 33P043- showed that the phosphate addition was taken up in < 1 h, with small particles (< 3 pm) containing 90% of the isotope. The inorganic P addition represented an approximate tripling of the particulate P concentration compared to the lake situation; the food addition amounted to more than a lo-fold increase in particulate P. From the final P analyses, we calculate that the zooplankton addition per se amounted to - 1 pg P liter- l. The food enrichment consisted of algae from a mixed culture of cryptomonad species at the equivalent of 10 pg Chl a liter-l and bacteria from a Pseudomonas strain isolated from the same locality at a final concentration of - 5 X lo6 cells ml-l. Specimens for C and N analysis were placed in preweighed tin capsules; preweighed polycarbonate capsules were used for the P analyses. Dry weights of the samples were measured on a Mettler ME30 microbalance after drying overnight at 60°C. Five-ten blank capsules were carried through the procedure to correct for differences in air humidity and drift in the calibration of the weighing equipment. C and N contents were measured on a Carlo-Erba CHN 1106 elemental analyzer. P analyses were performed in 7-ml scintillation minivials. All capsules, vials, and screwcaps were cleaned by soaking in antimony-molybdate solution and rinsing twice in double-distilled water. Samples were first oxidized 809 overnight with 200 ~1 of H202 at room temperature to make the exoskeleton more hydrophilic and to avoid incomplete digestion of animals floating on the surface. The samples were then digested in 2 ml of K&O8 solution (10 g liter-l) for 1 h at 120°C. If we assume that 2 mol of K&O8 is needed to oxidize an amount of organic C equivalent to 1 mol of CO*, the amount added would be sufficient to digest about sixfold the average sample dry weight (DW). Tests with animals reared on 33P-labeled food showed insignificant amounts of radioactivity in the exoskeleton residues after this digestion procedure. Standards were prepared by adding O-50~1 quantities of a stock orthophosphate solution (100 mg P liter- ‘) to minivials containing the empty polycarbonate capsules used as blanks in the weighing procedure. Letting the vials stand uncapped overnight at room temperature was sufficient to evaporate the added water. All standards were carried through the same digestion procedure as the samples. The rest of the analysis closely followed standard molybdate-blue methods for analysis of orthophosphate. The antimony-molybdate complexing reagent and the ascorbic acid reductant were prepared to yield correct final concentration after 200 ~1 was added to each solution to give a nominal final sample volume of 2.6 ml. The absorbance at 880 nm in l-cm cuvettes was linear with added orthophosphate over the whole range of O-5 pg P vial- l. As standards were prepared in terms of absolute amounts per vial instead of concentrations, the results were unaffected by any systematic water loss due to evaporation during digestion. P content was generally more variable than N and C contents in the field samples of all zooplankton species (Fig. 2). The comparison circles in the lower panels of Fig. 2 show that there were more significant interspecific differences in P content than in C and N contents. The species could tentatively be ranked, as done in Fig. 2, with decreasing C and N content and increasing P content as A. denticornis, H. saliens, B. longispina, H. gibber-urn, D. brachyurum, and D. longispina. One-way ANOVA indicated significant variation among species Notes 810 % Carbon % Phosphorus % Nitrogen 8 I 10 I I Acanthodiaptomus I i 0.6 I 12 I : I III 1.0 I 1.4 I 1.8 I Ii Heterocope Bosmina I Holopedium I I::! : Diaphanosoma I : i .: Ha-i I :::I 1:::: I Daphnia Fig. 2. Box-and-whisker displays of distributions of all field samples by zooplankton species and element (C, N, and P as percent of dry wt). Boxes indicate medians and the middle two quartiles; whiskers indicate the limits of the lO-90% percentiles. Box heights are proportional to sample sizes. Lower panels show comparison circles among species within an element; two distributions are considered different at a 95% C.L. if their circles are disjunct or have an outside angle of intersection ~90”. for all three elements (C: F5,96 = 4.93, P = 0.00 12; N: F5,94= 16.6, P= 0.0001; P: F5,101 = 83.1, P < 0.000 l), but tests by multiple Scheffe comparisons showed that many of the differences between adjacent species were not significant at the 5% level. In the laboratory experiments, the starvation treatment gave negligible egg production and rapidly increasing mortality in D. longispina by the end of the experiment. Phosphate addition alone did not change the egg production rate in any species, al- though animals fed with algae and bacteria increased egg production by threefold-fivefold compared to the field situation. This result makes it likely that secondary production at the time of the experiment was limited by food quantity and not food quality in terms of P content. The results from the experimental treatments (Fig. 3) did not differ significantly from the field samples in B. longispina (F3,26= 0.59, P = 0.63) and D. longispina (F3,45= 1.65, P = 0.19), but a significant difference was found in H. gib- % Phosphorus of dry weight 0.5 I I 1.0 I I 1.5 I I 0.5 I I 1.0 I I 1.5 I 0.5 1.0 1.5 2.0 - Food +P + Food Daphnia Holopedium Bosmina Fig. 3. Box-and-whisker displays of distributions of P contents in all samples from the laboratory by zooplankton species and treatment. Details same as for Fig. 2. experiments Notes 811 Heterocope E .o, I:: m :: t 1 g a% 6 1.5~- I Holopedium 1 I I Acanthodiaptomus ! Daphnia I May Jun Jul Aug Sep Ott May Jun Jul Fig. 4. Seasonal variation in P content in the zooplankton species investigated. of replicates-0 (range of replicated measurements indicated by vertical bars). berum (F3,27= 6.07, P = 0.0027). The most significant effect on H. gibberum was due to phosphate addition, which might be caused by uptake of inorganic P by the microflora attached to the gelatinous envelope of this species (Hessen et al. 1990). Excluding this treatment from the analysis showed no significant difference between the other treatments and the field observations (F2,23= 2.60, P = 0.096). Both seston and zooplankton composition showed the highest variability in P content. There was a clear seasonal trend in seston P content with low P : C in spring and high P : C in autumn (Fig. 1). Most zooplankton species showed some temporal variation (Fig. 4) that could not be explained by intraspecific variability or analytical errors, but the lack of correspondence among species makes it unlikely that this variation is the result of a common response to changes in the seston P : C ratio. At least for the copepods, we suspect that some of Aug Sep Single samples-O; Ott means the temporal pattern is related to specific life-history phenomena. Seasonal changes in C and N content are well documented in marine copepods from temperate and boreal areas (see Bamstedt 1986). The most pronounced variation in boreal species with univoltine life histories seems to be connected with lipid allocation strategies for surviving winter, so that one would expect less variability in freshwater species that survive the winter as resting stages. Baudouin and Ravera (1972) found no evidence of a seasonal pattern in the chemical composition of Daphnia hyalina from oligotrophic Lago di Monate. Behrendt (1990) found some temporal variability in zooplankton chemical composition in Grof3er Miiggelsee, but his results were based on total zooplankton samples, so the variation might be attributable to changes in species composition. Lehman and Naumoski (1985) reported that Daphnia pulex fed P-sufficient green Notes 812 Table 1. Summary of published measurements of P content in Daphnia species. Values from Vijverberg and Frank (1976) were recalculated assuming that total organic matter measured by chemical oxygen demand equals dry weight minus 7% chitin and 10% ash. Mean D. pulex D. pulex D. pulex D. hyalina D. hyalina D. rosea D. galeata 1.53 1.25 1.53 1.12 1.66 1.80 1.11 SD n Reference 0.06 0.32 0.23 0.10 0.17 0.21 0.14 3 56 5 30 9 60 5 Birge and Juday 1922 Lehman 1980 Langeland et al. 1985 Baudouin and Ravera 1972 Vijverberg and Frank 1976 Peters and Rigler 1973 Langeland et al. 1985 algae had a higher P content than individuals reared on P-deficient algae. Their conclusion was based on changes in the log-log regression of P per individual on individual length, with varying P status in the food algae. When comparing freshly molted individuals without eggs, the length-weight relationship in Daphnia is unaffected by food conditions (Lynch 1989). Without this precaution, this allometry can be quite variable and has often been used as an indicator of the prevailing growth conditions (e.g. Duncan 1985). The results of Lehman and Naumoski (198 5) could therefore also be interpreted as a change in the length-weight relationship caused by improved growth conditions, instead of a change in P content. Such an interpretation is supported by the prevalence of noneggbearing females in their low-P treatments (Lehman and Naumoski 1985, figure 1). The N and C contents we found all fall within the observed range in marine copepods as reviewed by BAmstedt ( 1986, tables 1.11 and 1.12), although a substantial number of our P measurements are above those reported in marine copepods (Bamstedt 1986, table 1.13). On the other hand, the mean P content in the two Calanoid copepods we considered (0.6 5 + 0.19% P of DW, n = 33) is close to the marine species investigated (0.76&O. 18% P of DW, n = 9). The close correspondence between the elemental ratios of the herbivorous-detrivorous A. denticornis, the carnivorous H. saliens, and their marine relatives suggests that a comparatively low P content might be a common property of Calanoid copepods. Observations of P content in several Daphnia species (Table 1) give a mean value of 1.43 +0.27% P of DW, which compares fa- vorably with the mean value of our estimates for D. longispina (1.47 + 0.17% P of DW). The consistently high P content across species and growth conditions indicates that it might be a generic property of Daphnia SPPUnicellular microplankton generally exhibit a flexible storage strategy with a large capacity for accumulating materials in excess of immediate demands for growth and maintenance (e.g. accumulation of polyphosphate under high P availability or carbohydrate under nutrient limitation). On the basis of the small amount of variation in zooplankton elemental ratios that could be attributed to changes in food conditions, such capacities seem to be limited in the species investigated. This result suggests that for many purposes the elemental composition of metazoan zooplankton can be considered constant and species-specific. Fixed elemental ratios put important constraints on the food utilization of zooplankton in that intake of a given element in excess of immediate demands must be disposed by increased excretion or by reduced assimilation of certain food components. This view is supported by the results of Lehman and Naumoski (1985), who found large differences between rates of gross P assimilation and P excretion for D. pulex fed algae with high and low P content. The predicted effect of food composition on nutrient recycling can be illustrated by partitioning the N : C, P : C plane into two regions demarcated by a straight line through the C : N : P ratio of the grazer (Fig. 5). Food items with C : N : P ratios in the upper region will have higher N : P ratios than that of the grazer and therefore contain more N than is required for balanced growth, im- Notes 0.16 -- 0.12 -- z E 8 2. .-0 EJ 0 z 0.002 0.004 0.006 0.008 0.010 P : C ratio (atoms) Fig. 5. C : N : P ratios in lake seston (0) in relation to the N : P ratios required for balanced growth (lines) in Acanthodiaptomus denticornis and Daphnia longispina. A and D indicate the measured C : N : P ratios of A. denticornis (212 : 39 : 1) and D. longispina (85 : 14: 1); R shows the Redfield ratio (106: 16: 1). plying an increased N : P ratio in recycled nutrients. Food items with C : N : P ratios in the lower region will have lower N : P ratios than that of the grazer and therefore contain more P than is required for balanced growth, implying a decreased N : P ratio in recycled nutrients. Figure 5 indicates that all the seston samples from the lake contain surplus N compared to the requirements of D. longispina, and that all except two samples contain surplus P compared to the requirements of A. denticornis. We thus expect D. longispina to have a higher N : P ratio in released nutrients than A. denticornis in the lake investigated. A general tendency for higher N : P ratio in recycled nutrients from zooplankton communities dominated by daphnids than from copepod-dominated communities can explain the results of Elser et al. (1988), who found distinct shifts between N- and P-limited phytoplankton growth accompanying changes in zooplankton community structure. Both experimental and field studies showed that N limitation prevailed in communities dominated by small species (mainly cyclopoid copepods), while dominance of large cladocerans (mainly daphnids) led to P limitation. This pattern is exactly what would be pre- 813 dicted if cyclopoids, as suggested by the results of Kahn and Siddiqui (197 l), are assumed to have the same kind of efficient P utilization as Calanoid copepods. Resource competition theory predicts that the N : P ratio of the nutrient supply can be a strong determinant for the species composition of the phytoplankton community (Kilham and Kilham 1984). It leads us to suggest that, in addition to the effects of selective grazing, zooplankton community structure could have an indirect selective force on the species composition of the phytoplankton community through the N : P ratio of the recycled nutrients. As cyanobacteria seem to be favored by low N: P supply ratios (Smith 1983), this might offer an additional explanation of the ability of daphnids to suppress cyanobacterial blooms. Tom Andersen Department of Biology University of Oslo P.O. Box 1069 Blindern N-03 16 Oslo 3, Norway Dag 0. Hessen Department of Biology University of Oslo P.O. Box 1050 Blindern References BAMSTEDT, U. 1986. Chemical composition and energy content, p. l-58. In E. D. S. Corner and S. C. M. O’Hara [eds.], The biological chemistry of marine copepods. Clarendon. BAUDOUIN, M. F., AND 0. RAVERA. 1972. Weight, size, and chemical composition of some freshwater zooplankters: Daphnia hyalina (Leydig). Limnol. Oceanogr. 17: 645-649. BEHRENDT, H. 1990. The chemical composition of phytoplankton and zooplankton in a eutrophic shallow lake. Arch. Hydrobiol. 118: 129-l 45. BIRGE, E. A., AND C. JUDAY. 1922. The inland lakes of Wisconsin. The plankton. 1. Its quantity and chemical composition. Wis. Geol. Nat. Hist. Surv. Bull. 64. 222 p. DUNCAN, A. 1985. Body carbon in daphnids as an indicator of the food concentration available in the field. Ergeb. Limnol. 21: 81-90. ELSER, J. J., M. M. ELSER, N. A. MACKAY, AND S. R. CARPENTER. 1988. Zooplankton-mediated transitions between N- and P-limited algal growth. Limnol. Oceanogr. 33: 1-14. HESSEN, D. 0. 1989. Factors determining the nutritive status and production of zooplankton in a humic lake. .I. Plankton Res. 11: 649-664. Notes 814 -, T. ANDERSEN,AND A. LYCHE. 1990. Carbon metabolism in a humic lake; pool sizes and cycling through zooplankton. Limnol. Oceanogr. 35: 8499. KAHN, J. A., AND A. 0. SIDDIQUI. 197 1. Water, nitrogen, and phosphorus in freshwater plankton. Hydrobiologia 37: 53 l-536. KILHAM, S. S., AND P. KILHAM. 1984. The importance of resource supply rates in determining phytoplankton community structure, p. 7-27. In Trophic interactions within aquatic ecosystems. AAAS Select. Symp. 85. LANGELAND, A.,J.I. KOKSVIK,ANDY.OLSEN. 1985. Post-embryonic development and growth rates of Daphnia pulex De Geer and Daphnia galeata Sars under natural food conditions. Int. Ver. Theor. Angew. Limnol. Verh. 22: 3 124-3 130. LEHMAN, J. T. 1980. Nutrient cycling as an interface between algae and grazers in freshwater communities. Am. Sot. Limnol. Oceanogr. Spec. Symp. 3: 25 l-263. -. 1984. Grazing, nutrient release, and their impacts on the structure of phytoplankton communities, p. 49-72. In Trophic interactions within aquatic ecosystems. AAAS Select. Symp. 85. -, AND T. NAUMOSKI. 1985. Content and turnover rates of phosphorus in Daphnia pulex: Effect of food quality. Hydrobiologia 128: 119-125. Lmnol. Oceanogr., 36(4), 199 1, 8 14-8 19 Society of Limnology 0 199 1, by the American and Oceanography, LYNCH, M. 1989. The life history consequences of resource depression in Daphnia pulex. Ecology 70: 246-256. OLSEN, Y., AND OTHERS. 1986. Dependence of the rate of release of phosphorus by zooplankton on the P : C ratio in the food supply, as calculated by a recycling model. Limnol. Oceanogr. 31: 34-44. AND K. ~STGAAFCD. 1985. Estimating release ra;es of phosphorus from zooplankton: Model and experimental verification. Limnol. Oceanogr. 30: 844-852. PETERS,R. H., AND F. H. RIGLER. 1973. Phosphorus release by Daphnia. Limnol. Oceanogr. 18: 821839. SMITH, V. H. 1983. Low nitrogen to phosphorus ratios favor dominance by blue-green algae in lake phytoplankton. Science 221: 669-67 1. STERNER, R. W. 1989. The role of grazers in phytoplankton succession, p. 107-170. In U. Sommer [ed.], Plankton ecology. BrocWSpringer. VLJVERBERG,J., AND T. H. FRANK. 1976. The chemical composition and energy contents of copepods and cladocerans in relation to their size. Freshwater Biol. 6: 333-345. Submitted: 1 April 1988 Accepted: 18 March 1991 Revised: 15 April 1991 Inc. An improved fluorescence method for the determination of nanomolar concentrations of ammonium in natural waters Abstract -An improved fluorescence method is described for measuring nanomolar concentrations of NH,+ in natural waters. This method is based on the conversion of NH,+ to NH, and subsequent diffusion of NH, across a microporous hydrophobic Teflon membrane into a flowing stream of o-phthaldialdehyde reagent to produce a fluorescent adduct. The product is detected fluorometrically with a lower detection limit of better than 1.5 nM. Up to 30 determinations h-l can be made. The method works well in freshwater or salt water. Field tests of the method in the Dry Tortugas and Gulf Stream gave NH,+ concentrations that ranged from 18.0 nM in Gulf Stream waters to 2,254.7 nM in interstitial waters Acknowledgments This work was supported by the National Science Foundation through grant OCE 86-20249. I thank Capt. Millender and the crew of the RV Bellows for assistance during the field tests and A. Holloway for preparing the figures. I thank M. A. Brzezinski and J. H. Sharp for reviews. from coralline reef sands. The method can be used to measure near real-time NH,+ concentrations in situations where it was previously difficult or impossible. The measurement of NH4+ in natural waters is key to understanding several aspects of the aquatic nitrogen cycle (Carpenter and Capone 1983). Often this measurement has been hampered by detection limits or the time involved in determining nanomolar concentrations of NH4+. Brzezinski (1987, 1988) has developed and applied a method for calorimetric determination of nanomolar concentrations of NH,+ using a solvent extraction technique. Although his method has a detection limit of 3.5 nM, the procedure of extraction and analysis is slow and labor intensive, allowing only 30 samples to be processed in an 8-h day (Brzezinski