Carbon and Nitrogen Balances in Ocean Tank at the New Jersey State Aquarium Régulation des flux de carbone et d'azote dans le bassin «Océan» de l'Aquarium du New Jersey Gordon GRGURIC1, Christopher J. SONDEY1 and Brian M. DUVALL2 1 Marine Science Program, The Richard Stockton College of New Jersey, Pomona, NJ 08240, USA 2 New Jersey State Aquariums, 1 Riverside Drive, Camden, NJ 08103, USA ABSTRACT A variety of empirical and calculated data from the largest tank at the New Jersey State Aquarium were used to quantify the fluxes of carbon and nitrogen before and after the installation of denitrification in this facility. Before denitrification, the stock of dissolved inorganic carbon (DIC) in Ocean Tank exhibited a decrease of 6.9 kg C/month and sodium bicarbonate had to be added to maintain DIC in steady state. Nitrogen budget in Ocean Tank before denitrification is in contrast to that of carbon, and it shows an increase of 4.8 kg N/month in the form of nitrate. The use of methanol for denitrification has resulted in a flux of 26.3 kg C/month into the aquarium and, as predicted, an increase in Ocean Tank DIC stock has been observed without any additions of sodium bicarbonate. RESUME Une multitude de données empiriques et calculées, issues de la plus grande cuve de l'Aquarium du New Jersey, ont été utilisées pour quantifier le flux de carbone et d'azote avant et après l'installation d'un système de dénitrification sur ce bac. Avant l'installation du système de dénitrification, la réserve de carbone inorganique dissous (DIC) présentait une décroissance moyenne de 6.9 kg/mois et du bicarbonate de soude devait être ajouté pour maintenir le DIC à un niveau constant. Le bilan d'azote de la cuve Océan avant l'existence d'un système de dénitrification était inversé par rapport au carbone, avec une augmentation de près de 48 kg N/mois sous la forme de nitrate. L'utilisation de méthanol comme source de carbone pour la dénitrification a généré un flux de carbone de 26.3 kg C/mois dans l'aquarium et un accroissement du DIC a été observé sans ajout de bicarbonate de sodium. Bulletin de l’Institut océanographique, Monaco, n° spécial 20, fascicule 1 (2001) INTRODUCTION Ocean Tank at the New Jersey State Aquarium has a volume of 2.87 million liters, which makes it one of the largest aquarium tanks on the East Coast of the United States. The environment on display mimics the continental shelf adjacent to the New Jersey coast, including the Hudson River Canyon. The tank houses about 40 different fish species, ranging from blueback herrings and mullets to sand tiger sharks and rough-tail stingrays. The medium, in which these species live, is artificial seawater of salinity 28-30 g/kg and temperature of 20C. Flow dynamics through Ocean Tank involve surface skimming to produce a total flow rate of 16,000 L/min that is delivered to twelve parallel sand filters and treated afterward in a bio-filter. A small fraction (less than 10%) of the total flow is ozonated in a separate line. The filtered and disinfected water is reintroduced to the tank through a silica quartz gravel bed on the aquarium floor. The volume of the entire system re-circulates in about 3 h. We used a variety of empirical data, collected since Ocean Tank opened, to determine, directly or indirectly, the magnitudes of carbon and nitrogen fluxes in this system. We compare the steady state of carbon to the non-steady state of nitrogen and examine how the installation of a biological denitrification system has affected the balances of these two elements in the aquarium. RESULT AND DISCUSSION The largest carbon reservoir in Ocean Tank seawater is dissolved inorganic carbon (DIC), which is defined as the sum of CO2 (aq), HCO3- and CO32- species (Libes, 1992) and serves as a buffering system for seawater pH. In ambient ocean, the size of this reservoir is 30 times greater than that of dissolved and particulate organic carbon (Millero, 1996). Occasional measurements of total organic carbon in Ocean Tank show a concentration of less than 60 μM. This value is essentially the concentration of dissolved organic carbon (DOC), because recirculation and filtering quickly remove most particulates. DIC in Ocean Tank can be determined from pH and total alkalinity measurements, where the average values of those quantities in Ocean Tank are 7.65 and 2.46 meq/L, respectively. Carbonic acid equilibria in seawater as given in Millero (1996) can be used to show that these values translate to a DIC concentration that is at least 40 times greater than the DOC concentration in the system. Therefore, the DOC reservoir was considered insignificant relative to the other carbon reservoirs and fluxes in this study. The main source of carbon to Ocean Tank is food given to the fish in the tank. This food consists of raw seafood as well as processed fishmeal. The feeding records show that, on average, 26.1 kg of raw seafood and 1.3 kg of fishmeal are given each day. The elemental composition of nitrogen and phosphorus in the fishmeal can be used to compute the weight fraction of carbon, using Redfield ratio (Redfield et al., 1963). For raw seafood, the amount of carbon can be Bulletin de l’Institut océanographique, Monaco, n° spécial 20, fascicule 1 (2001) determined from the ratio of particulate organic matter to particulate organic carbon (Pilson, 1998) for dry, salt-free organic matter. The amount of carbon thus calculated is 9.3 kg/day from raw seafood, and 0.6 kg/day from fishmeal. These values can be combined to yield a flux of 296 kg C/month from food sources. Continuous formation of white precipitates has been observed on artificial rocks in Ocean Tank. These precipitates were found to be carbonaceous in nature, with Mg and Ca as the principal cations. The carbon flux into these precipitates can be calculated if their formation rate is known. This rate can be determined from the magnesium budget in Ocean Tank, which exhibits non-conservative behavior, as evidenced by the significantly lower Mg/Cl ratio in Ocean Tank relative to the ratio in freshly prepared artificial seawater (Figure 1). Precipitation of these cations as carbonate was computed to remove 4.2 kg C/month from Ocean Tank seawater. Figure 1. Three-year averages and standard deviations for Mg/Cl ratios in Ocean Tank and in freshly prepared artificial seawater in Salt Water Tank There are several other carbon fluxes in Ocean Tank that were not yet discussed. All of them are net carbon losses and they are specifically: (1) outgassing of carbon dioxide, (2) excretion and removal of fecal pellets, and (3) retention of organic carbon for the growth of aquarium organisms. These fluxes were not individually quantified due to the difficulty in obtaining accurate measurements and/or interpreting them. However, their net magnitude can be calculated from the known fluxes, if carbon in the system is in steady state. Steady state carbon conditions in the aquarium are achieved through occasional additions of sodium bicarbonate to the tank. The magnitude of this flux can be determined from sodium bicarbonate addition records to Ocean Tank, given in Table 1. The difference between DIC concentrations calculated from initial and final pH and Bulletin de l’Institut océanographique, Monaco, n° spécial 20, fascicule 1 (2001) alkalinity values in Table 1 is 1.25%, so the sodium bicarbonate addition record for this period can be interpreted as that needed to maintain carbon in steady state. From the total mass of sodium bicarbonate added and the time elapsed, this flux is calculated as 8.6 kg C/month. ______________________________________________________________________________ Table 1: Record of pH, total alkalinity and sodium bicarbonate additions to Ocean Tank over a three month period ______________________________________________________________________________ Date pH Total Alkalinity (meq/L) December 18, 1997 7.75 2.50 December 23, 1997 7.78 2.51 January 6, 1998 7.81 2.39 January 20, 1998 7.77 2.29 January 21, 1998 7.76 2.25 January 22, 1998 7.74 2.24 February 5, 1998 7.62 2.08 February 19, 1998 7.61 2.00 March 4, 1998 7.57 1.84 March 11, 1998 45.4 kg NaHCO3 added March 12, 1998 45.4 kg " " March 13, 1998 45.4 kg " " March 14, 1998 45.4 kg " " March 17, 1998 7.72 2.46 ______________________________________________________________________________ To understand why additions of sodium bicarbonate are necessary in a closed system, heterotrophic respiration in seawater needs to be considered, and the subsequent decrease in pH due to equilibration of the released carbon dioxide (eq. 1 and 2). CO2 + H2O <═══════> H+ + HCO3- (1) HCO3- <═══════> H+ + CO32(2) Figure 2 shows pH and alkalinity in Ocean Tank during a three-month period, when no sodium bicarbonate was added. The continuous decrease in both parameters is due to acidity produced during bacterial nitrification reactions in aquarium bio-filters. The data shown in Figure 2 are in contrast to ambient marine observations (Park, 1969; Goyet and Brewer, 1993), and a carbon loss of 6.9 kg/month has been computed. This result is in reasonable agreement with the flux of carbon through additions of sodium bicarbonate needed to maintain DIC in steady state (previously shown as 8.6 kg C/month). Bulletin de l’Institut océanographique, Monaco, n° spécial 20, fascicule 1 (2001) Figure 2. Changes in pH (circles) and alkalinity (squares) over a three month period when no sodium bicarbonate was added to Ocean Tank For the first several years of its operation, Ocean Tank seawater exhibited a continuous increase in its nitrate concentration. The rate of nitrate concentration increase translated to a nitrogen addition flux of 4.8 kg N/month. Concerns about nitrate toxicity in Ocean Tank prompted the installation of a biological denitrification system in 1998. Biological denitrification under controlled conditions has been employed to decrease nitrate concentrations in other large seawater aquaria (Grguric and Coston, 1998). Denitrification in Ocean Tank is separate from the main water circulation and treatment loop, and the system hosts facultative anaerobic bacteria, which use nitrate as an oxidizing agent for their metabolic processes. Methanol is used as a source of organic carbon for the bacteria and the net denitrification reaction (Jeris and Owens, 1975) is given in equation (3): 6 NO3- + 5 CH3OH ────────> 3 N2 + 5 CO2 + 7 H2O + 6 OH- (3) Since 1998, nitrogen in Ocean Tank has a sink as well as a continued source in animal feed, and its concentration should eventually reach a steady state. The effect of denitrification on carbon fluxes in Ocean Tank is particularly interesting, and can be seen from the right side of equation (3). The production of hydroxide ions leads to an increase in pH and therefore, equilibration of the released carbon dioxide means that a relatively small fraction will be lost through outgassing, and a much larger fraction will remain in solution (largely as HCO3- ions). Bulletin de l’Institut océanographique, Monaco, n° spécial 20, fascicule 1 (2001) Denitrification is thus expected to serve as a net source of carbon to the aquarium, and the magnitude of this flux has been determined from DIC concentrations in denitrification influent vs. effluent. The resulting flux of 26.3 kg C/month is greater than either the observed carbon loss in the aquarium (6.9 kg/month) or the amount of carbon needed to maintain steady state before denitrification (8.6 kg/month). The carbon stock in Ocean Tank is therefore expected to increase over time, and during denitrification, no sodium bicarbonate has to be added to the aquarium seawater. Thus, both carbon and nitrogen balances in Ocean Tank have been fundamentally affected by the presence of a biological denitrification environment. ACKNOWLEDGEMENTS The authors wish to thank Mark Kind and Frank Steslow of the New Jersey State Aquarium, as well as David Vieira of Richard Stockton College for discussions and valuable assistance during this study. REFERENCES GOYET C. and BREWER P., 1993.- Biogeochemical properties of the oceanic carbon cycle-. Modeling Oceanic Carbon Interaction, Vol. 1, J. Willebrand and D. L. T. Anderson (eds.). Springer Verlag, New York, pp. 271-297. GRGURIC G. and COSTON C. J., 1998.- Modeling of nitrate and bromate in a seawater aquarium-. Wat. Res. 32, 1759-1768. JERIS R. S. and OWENS R. W., 1975.- Pilot scale, high-rate biological denitrification-. J. Wat. Pollut. Contr. Fed. 47, 2043-2057. LIBES, S. M., 1992.- An introduction to marine biogeochemistry. John Wiley and Sons, New York, pp. 242-261. MILLERO F. J., 1996.- Chemical oceanography, 2nd ed. CRC Press, Boca Raton, FL, pp. 237-279. PARK P. K., 1969.- Oceanic CO2 system: an evaluation of ten methods of investigation-. Limnol. Oceanogr. 2, 179-186. PILSON M. E. Q., 1998.- An introduction to the chemistry of the sea. Prentice Hall, Upper Saddle River, NJ, pp. 259-299. REDFIELD A. C., KETCHUM B. H. and Richards F. A., 1963.- The influence of organisms on the composition of seawater-. The Sea, Vol. 2, M. N. Hill (ed.). Interscience Publishers, New York, pp. 26-87. Bulletin de l’Institut océanographique, Monaco, n° spécial 20, fascicule 1 (2001) Bulletin de l’Institut océanographique, Monaco, n° spécial 20, fascicule 1 (2001)
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