Aquaculrural Engineering 3 (1984) 207-220

The Type of Activated Carbon Determines How Much Dissolved Organic Carbon is Removed from Artificial Seawater*

S t e p h e n Spotte and G a r y A d a m s
Mystic Marinelife Aquarium, Sea Research Foundation Inc., Mystic, Connecticut 06355, USA

ABSTRACT Four granular activated carbons (GACs) made of different materials were tested for removal of dissolved organic carbon (DOC) from artificial seawater of a recirculated aquarium. After 70 days in a continuous flow experiment, comparative removal data {grams of GAC required to remove I g o]'DOC) were coconut shell (491), hardwood (84.4), anthracite (837) and bone char {383), indicating the superior performance of hardwood. Scanning electron microscopy showed that microbial colonization of a sample material (hardwood) was slight and occurred exclusively at the surface. Biological enhancement of GAC was considered to be unimportant as a mechanism for DOC removal.

INTRODUCTION Granular activated carbon (GAC) is commonly used in drinking water and wastewater treatment to remove organic carbon (US EPA, 1973; McCreary and Snoeyink, 1977; Suffet, 1980; Constantine, 1982; Roberts and Summers, 1982). Saler and Slabbert (1980) evaluated activated carbons made of different materials to determine which were most effective in wastewater reclamation. Comparable studies in closed (recircutated) aquarium systems have not been done, despite concern that some organics appearing in natural and captive waters as metabolic by-products of animals and plants are toxic (Sieburth and Jensen, 1969,
* Contribution no. 48, Sea Research Foundation Inc. 207 Aquacultural Engineering 0144-8609/84/S03.00 Elsevier Applied Publishers Ltd, England, 1984. Printed in Great Britain

Science

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Stephen Sporre. Gary Adams

1970), immunosuppressive (Perlmutter et al., 1973), and limit growth and reproduction (Lake, 1967; Yu and Perlmutter, 1970; Pfuderer et al., 1974: Chen and Martinich, 1975).

METHODS AND MATERIALS Four activated carbons packaged in sealed, waxed paper bags were obtained from the manufacturer (Barnebey-Cheney, Columbus, Ohio, USA). Materials and manufacturer's designations were: coconut shell (AC 2143), hardwood (NB L-2175), anthracite coal (302-9342) and steamed bone char (485-0098). The materials were crushed and sieved through a series of standard screens. Grains between 1190 and 2000 um were retained. Dry masses of the materials were then determined by weighing them in 1 liter lots. Results are given in Table 1. The source of water was a 113 400 liter recirculated exhibit tank at Mystic Marinelife Aquarium filled with modified Segedi-Kelley Medium, an artificial seawater (Spotte, 1979). The exhibit is maintained at ambient temperature (~18C) and displays large elasmobranchs and teleosts indigenous to Long Island Sound. Filtration is accomplished by a subgravel filter powered by 18 airlift pumps. The filtrant is a layer of crushed oyster shells 30 cm deep. Subgravel filtration is augmented by a 76 cm diameter rapid sand filter. No other treatment or processing is provided. The experiment was designed in a continuous flow configuration. Water was pumped from the exhibit through the experimental apparatus (Fig. 1). The influent line consisted of ~ 6 m Tygon tubing (1.27 cm

TABLE 1

Results of GAC Treatment

Coconut Hardwood Anthracite Bone char

Dry mass of GAC, g Average flow rate, ml min-I EBVs, 70.43 days DOC removed, g g GAC/g DOC removed

624.3 23.69 2403 1-27 491

261-0 23.44 2377 3.09 84.4

862.1 23.99 2433 1.03 837

765.3 23-54 2387 2.00 383

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Experimental apparatus.

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Stephen Spotte, Gary Adams

ID, 0.3 cm wall thickness), one end of which was submerged to the bottom of an airlift pump. The flow of air in that airlift was stopped for the duration of the experiment. The other end was inserted through a three-hole rubber stopper in a 1 gallon (US) glass bottle that served as an air trap. Both ends were covered with plankton netting (63 ~m mesh). The air trap was at a higher elevation than the pump and flasks, which were at the same level. The small amount of air that collected in the neck of the bottle was removed periodically through 76 cm of polyethylene tubing (0.02 cm ID) attached to a 50 ml syringe. A pinch clamp allowed the syringe to be disconnected to purge the air. The third hole served as the effluent line from the air trap (influent to the pump heads). It was the same size and material as the influent line. A manifold was made by joining two no. 6 neoprene stoppers (one two-hole, the other four-hole) with a spacer in-between and taping the stoppers together. The effluent line from the air trap was inserted in the two-hole stopper; the other hole held a length of polypropylene tubing identical to the one in the air trap. It was also equipped with a pinch clamp and syringe and served as a source of control water. Four sections of rigid polypropylene tubing (3 m m ID) were inserted in the four-hole stopper for attachment of ~ 1 8 0 cm o f C-Flex Tubing (0.48 cm ID, number 6424-45, ColeParmer Instrument Co., Chicago, USA). Each length was connected to a pump head (Masterflex Standard Pump Head, model 70t 5-20, ColeParmer Instrument Co.). The quadruple heads were driven in tandem by a single peristaltic pump (Masterflex 'Unified' Drive Pump, model 7520-30, Cole-Parmer Instrument Co.). A length ( ~ 5 0 cm) of polypropylene aquarium tubing (0.3 cm ID) was inserted in the end of each section of C-Flex Tubing and connected to standard glass laboratory tubing (0-3 cm ID). The glass tubing was fired and each piece was bent into an L shape (23-5 cm straight tubing plus 1.5 cm after a 90 bend). The lengths of glass tubing were inserted through one-hole neoprene stoppers (no. 8) and placed inside 1 liter glass filter flasks that served as GAC contactors. Afterwards 1 liter of each sieved GAC was washed with deionized water and placed in a flask. A plug of glass wool inserted in each flask arm from the inside prevented particles of GAC from contaminating the samples. The GAC was then sterilized by autoclaving the flasks at 120C and 103 kPa for 30 rain. Water flowed through the flasks, out of the arms, and back to the exhibit. To inhibit algae f r o m growing in the apparatus and leaching organic compounds the air trap was covered with black polyethylene, and all tubing was covered with black electrical tape.

Dissolved organic carbon removal from artificial seawater

211

Glassware was washed sequentially in solutions of 3% KMnO4 in 10% NaOH and 1.5 HC1 in 3% Na.,SO3, then rinsed with distilled water to remove contaminant organics. In addition, sample bottles and glass filters were precombusted at 450C overnight in a muffle furnace. Filter flask stoppers were wrapped in new aluminum foil to prevent possible contamination from the neoprene. Only the polyethylene tubing was not treated, but water from the exhibit tank was allowed to flow freely through it for 2 days to wash out any particulate or soluble material. The apparatus was kept in continuous operation for 78 days. Samples from each flask and the control were collected on alternate days at 1000 h for the first 70 days. To collect the control sample the pinch clamp was removed and water was drawn into a 50 ml syringe and discarded. Afterwards 50 ml were collected in the syringe. Samples of treated water were collected and filtered directly by holding a membrane filter apparatus (Millipore Corp., Bedford, Massachusetts, USA) under the arms of the flasks. The water was filtered through 0.3/am sintered glass filters (Gelman Glass Filters, type AE, no. 6 t 631, 47 ram, distributed by VWR Scientific, Boston, USA). The first ~ 1 0 ml of filtrate were flushed to waste; the next ~ 5 0 ml were collected in a 240 ml glass bottle. The bottle was capped with new aluminum foil and frozen at - 3 2 C . This procedure causes no loss of TOC (total organic carbon) during storage (Otson et al., 1979). The glass filters were used only once, and the filter apparatus was cleaned between samples by flushing with distilled water. The analytical method used to determine organic carbon has been described previously (Adams and Spotte, 1980, 1982; Spotte and Adams, 1982), except that samples were prefiltered. Dissolved organic carbon (DOC) was measured with a TOC analyzer (Oceanography International Corp., College Station, Texas, USA), using an adaptation of the wet oxidation method of Menzel and Vaccaro (1964). Detailed procedures for use of the equipment were given by Airey and Hogan (1980). Most organic compounds appear to be oxidized completely to CO2 (Williams, 1966; Collins and Williams, 1977). The definition of DOC is arbitrary, but here we define it as all material that passed through a 0-3/am filter. Thawed samples were shaken and triplicate 5 ml volumes were pipetted into 10 ml precombusted ampoules containing 0-25 g potassium persulfate (K2S2Os). The CO2 produced by acidification of available carbonate was removed by sparging with oxygen for a minimum of 6 rain. Ampoules were then sealed in

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Stephen Spotte, Gary Adams

a manner preventing entry of any combustion gases. Sealed ampoules were placed in a pressure vessel and oxidized for 3 h at 103C (_5C), as modified b y Kerr and Quinn (1975) from the original method of Menzel and Vaccaro. After cooling, CO2 generated as a reaction product was purged into an infrared analyzer (Horiba PIR-2000, Oceanography International Corp.), and the o u t p u t was integrated. The CO: concentration was determined from a standard curve produced by oxidizing known amounts of primary standard ~ a d e potassium hydrogen phthalate (Fisher P-243) dried at 105C for at least 18 h. Reagent blanks were made according to standard techniques, and all values were corrected for organic c o m p o u n d s in the reagents or ampoules.

RESULTS 85 water samples were taken. On 15 occasions one ampoule o f a triplicate set broke; in one case two ampoules broke. In four other instances one value of a triplicate set was rejected by the t-test. The data thus consisted of 234 DOC measurements. The mean of the standard deviations was 0.046 mg DOC liter -1 as determined from standard deviations of the 65 samples measured in triplicate. Flow through the flasks was expressed as e m p t y bed volume (EBV), defined as the bulk volume of GAC added to a f l a s k - in this case 1 liter. Average flow rates are shown in Table 1. The total volumes delivered by the four pump heads deviated little: mean = 2400 EBVs, standard deviation = 24-5 EBVs and relative standard deviation = 1.0%. The four samples of GAC differed noticeably in adsorptive characteristics both in the total mass of DOC adsorbed and adsorption rate (fraction adsorbed as a function o f time). The mass of DOC removed ranged from 1.03 g (anthracite) to 3.09 g (hardwood), as shown in Table 1. The mass of GAC required to remove 1 g DOC ranged from 84.4 g (hardwood) to 837 g (anthracite), or almost an order of magnitude. Differences in the fraction of DOC adsorbed by each material as a function of time are illustrated in Fig. 2. H a r d w o o d had removed a maximum of 73% of DOC in the influent water by day 2. Afterwards the concentration removed declined, gradually, to 27% on day 70. In contrast, anthracite removed a maximum of 64% within 2 tl o f the start o f the experiment, but by day 4 the amount removed had declined to 29% and finally to 7-5% on day 70. Bone char removed a maximum

Dissolved organic carbon removal from arrih'cial sea~varer

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Fig. 2. Massof DOC removed (rag liter -I )as a function of time for 70 days.

of 48% by day 6, and by day 70 the amount had declined gradually to 12%. Unlike the other materials, bone char appeared to desorb organic matter for the first day, causing the concentrations of DOC in the treated effluent to exceed the concentration in the influent. The adsorption pattern of coconut shell resembled that of anthracite. A maximum of 5 4 % of the DOC was removed on day 1 ; thereafter the amount declined rapidly to 9.6% on day 30 and remained essentially unchanged until day 70. The rate at which adsorptive capacity diminished was less for the more effective materials (hardwood and bone char). Hardwood was clearly superior to the rest: at 42 days ~ts performance still exceeded the peak performance o f coconut and anthracite (see below).

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Stephen Spotte, Gary Adams

DISCUSSION Maximum DOC removal by coconut shell and hardwood occurred at day 1.42, that of anthracite at day 0.65 and bone char at day 4.42. Such early peak performances were expected. Adsorption rate is a mass transfer process, limited by factors that control diffusion. Foremost of these is the adsorbate concentration of the untreated influent. Before adsorption from a liquid to a solid phase can occur a film of liquid must form on the surfaces of the adsorbent. The greatest adsorption rate takes place immediately after 'wetting' because the concentration gradient for diffusion is steepest. Adsorption rate diminishes rapidly as adsorbate concentrations in the two phases (liquid and solid) approach steady state. In the 70 days of the sampling period 8.5% of the volume of the exhibit was filtered through the four flasks and returned to the water system. In this period 7.39 g DOC were removed, representing 2.1% DOC in the exhibit water at any time. The fact that treated effluent was returning to the aquarium exhibit where it comprised a tiny fraction of the largely untreated reservoir did not affect the results, as illustrated by the small variation in the DOC concentration of the control (untreated) water. Control water DOC was measured 17 times in triplicate and values ranged from 3.14 to 3.53 mg liter-~. The mean concentration was 3.30rag liter-1 (standard deviation= 0-097 mg liter -1, relative standard deviation = 2.9%). When the data are plotted (Fig. 3) they illustrate tile remarkable capacity of tile biological filter for degradation of organic matter (i.e. DOC does not increase significantly with time). Under certain conditions the microbiological films that form on GAC grains measurably enhance TOC reduction in wastewater (Maqsood and Benedek, 1977; Ying and Weber, 1979; Lowry and Burkhead, 1980; Lin, 1983; Li and DiGiano, 1983). The usual explanation for why this happens is the large surface area on GAC grains for attachment and growth of microorganisms (American Water Works Association, 1981), but recent research indicates that surface area is not the determining factor. Bancroft et al. (1983) studied removal of TOC from wastewater. They found no statistical difference in its microbial removal on GAC compared with silica sand. The latter material is non-porous and has a much smaller surface area. Peel and Benedek (1983) reported that the

Dissolved organic carbon remova? ?om arrihciai seawater

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presence of microorganisms in GAC beds had no effect on TOC reduction in simulated wastewater. They suggested that biological enhancement is limited to situations in which the organic carbon is biodegradable and sufficient oxygen is available. Scanning electron microscopy (SEM) was used to demonstrate how sparsely the surfaces of GAC grains were populated with microorganisms, and that the internal pores were devoid of cells. We subjected one o f our test materials (hardwood) to SEM on days 0, 49 and 78 (Figs 4 through 7). Visible microorganisms colonized only the surfaces of the material. No bacteria or protozoans were found inside the used GAC, despite its extensive internal pore structure. Physical adsorption and biological degradation occur simultaneously in GAC beds, and their specific effects are difficult to distinguish without influencing process conditions (Peel and Benedek, 1983). We made no attempt to determine how much DOC removal was related directly to microbial activity. The data suggest that removal of DOC under conditions of our experiment was exclusively a physical adsorption process. Biological enhancement does not appear to have been a factor. Our untreated influent was possibly nutrient-limited, hypoxic, or both, which could account for the unexpectedly low degree of colonization. A more likely explanation is the vigorous activity of the biological filter, which may have reduced the concentration of b i o d e g a d a b l e

216

Stephen Spotte, Gary Adarns

Fig, 4.

SEM of unused hardwood GAC. Loose material is surface 'fines', (525 x .)

Fig. 5.

SEM of tile surface of used hardwood GAC at day 49. (520 x .)

Dissolved organic carbon removal f , o m arrificiai seawater

2 17

Fig, 6. SEM of the surface of used hardwood GAC at day 78. Visible rnicroorganisms include cocci, rods and stalked bacteria (Caulobacter-like). some appearing to be embedded in extracellular material or attached by it. Not visible in this photomicrograph but seen m others were choanoflageltates and small r.estate amoebae, which probably consume bacteria, t 2350 .~. I

DOC b e f o r e the influent w a t e r reached the GAC flasks. T h e e x t e n t o f any such activity was not discernible on a short-term basis, as we learned f r o m a brief, ancillary e x p e r i m e n t . Water was sampled at five locations just above the filter bed and in five o f the airlifts (i.e. below the filter bed) to d e t e r m h l e it" the decrease in DOC c o n c e n t r a t i o n across tile layer o f crushed o y s t e r shells was significant. Each sample was a n a l y z e d in triplicate by the p r o c e d u r e s described previously. 10 m e a s u r e m e n t s were made above tile bed and 13 below it. T h e DOC c o n c e n t r a t i o n s averaged 1-905 mg liter -~ (standard deviation = 0 . 1 3 4 mg liter -1) and 1-822 mg liter < (standard deviation = 0.096 mg liter-~). respectively. At a 0.05 level o f significance we c a n n o t c o n c l u d e that the observed decrease is not due to chance.

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Stephen Spotre, Gary Adams

Fig. 7. SEM of the interior of used hardwood GAC at day 78. Note that the pores are perfectly clean and devoid of microorganisms, indicating that colonization occurs primarily on external surfaces. (223 x .)

AC KNOWLE DGEM ENTS Patricia M. Bubucis and Michael B. McHone provided technical assistance, and Joseph T. O'Neill and Trish LaPointe drew Figs 1, 2 and 3. James W. Atz, Joseph P. Bidwell, John D. Buck and Lee C. Eagleton reviewed the manuscript.

REFERENCES Adams, G. & Spotte, S. (1980). Effects of tertiary methods on total organic carbon removal in saline, closed-system marine mammal pools. Am. J. Vet. Res., 41, 1470-4. Adams, G. & Spottc, S. (1982) Removal of total organic carbon from marine mammal pool water by polymeric resins. Am. J. Vet. Rex.. 43,919-2l.

Dissolved organic carbon removal from artificial seawater

219

Airey, D. & Hogan, M. (1980). Methods for the determination of dissolved and particulate organic carbon in marine samples. Rpt. 127, Division of Fisheries and Oceanography, CSIRO, Cronulla, AustraUa. American Water Works Association (1981). An assessment of microbial activity on GAC. J. Am. Water Works Assoc., 73,447-54. Bancroft, K., Maloney, S. W., McElhaney, J., Suffet, I. H. & Pipes, W. O. (1983). Assessment of bacterial growth and total organic carbon removal on granular activated carbon contactors. AppL Environ. Microbiol., 46,683-8. Bouwer, E. J. & McCarty, P. L. (1982). Removal of trace chlorinated organic compounds by activated carbon and fb~ed-film bacteria. Environ. Sci. Technol., 16,836-43. Chen, L-C. & Martinich, R. L. (t975). Pheromonal stimulation and metabolite inhibition of ovulation in the zebrafish, Brachydanio rerio. Fish. Bull. (NOAA), 73,889-94. Collins, K. J. & Williams, P. J. LeB. (1977). An automatic photochemical method for the determination of dissolved organic carbon in sea and estuarine waters. Mar. Chem., 5,123-41. Constantine, T. A. (1982) Advanced water treatment for color and organics removal. J. Am. Water Works Assoc., 74, 310-13. Kerr, R. A. & Quinn, J. G. (1975). Chemical studies on the dissolved organic matter in seawater. Isolation and fractionation. Deep-Sea Res., 22,107-16. Lake, J. S. (1967). Rearing experiments with five species of Australian freshwater fishes. Aust. J. Mar. Freshwat. Res., 18, 137-53. Li, A. Y. L. & DiGiano, A. (1983). Availability of sorbed substrate for microbial degradation on granular activated carbon. J. Water Pollut. Contr. Fed., 55, 392-9. Lin, C-C. (1983). Application of granular activated carbon for water and wastewater purification. Diss. Abst. Int., 43, 3905-B. Lowry, J. D. & Burkhead, C. E. (1980). The role of adsorption in biologically extended activated carbon columns. J. WaterPollut. Contr. Fed., 52,389-98. Maqsood, R. & Benedek, A. (1977). Low-temperature organic removal and dentrification in activated carbon columns. J. Water Pollut. Contr. Fed., 49, 2107-17. McCreary, J. J. & Snoeyink, V. L. (1977). Granular activated carbon in water treatment. J. Am. Water Works Assoc., 69,437-44. Menzel, D. W. & Vaccaro, R. W. (1964). The measurement of dissolved and particulate carbon in seawater. Limnol. Oceanogr., 9, 138-42. Otsotu R., Williams, D. T., Bothwell, P. D., McCullough, R. S. & Tate, R. A. (1979). Effects of sampling, shipping, and storage on total organic carbon levels in water samples. Bull. Environ. Contam. Toxicol., 23, 311-18. Peel, R. G. & Benedek, A. (1983). Biodegradation and adsorption within activated carbon adsorbers. J. WaterPollut. Contr. Fed., 55, 1168-73.

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Perlmutter, A., Sarot, D. A., Yu, M-L. Filazzola, R. J. & Seeley, R. J. (1973). The effect of crowding on the immune response of the blue gourami, Trichogaster trichoptenls, to infectious pancreatic necrosis (IPN) virus. Life Sci.. 13,363-75. Pfuderer, P., Williams, P. & Francis, A. A. (1974). Partial purification of the crowding factor in Carassius auratus and Cyprinus carpio. J. Exp. Zool., 187,375-82. Roberts, P. V. & Summers, R. S. (1982). Performance of granular activated carbon for total organic carbon removal. J. Am. Water Works Assoc., 74, 113-18. Saler, A. & Slabbert, J. L. (1980). A preliminary comparison between various granular active carbons for water reclamation. Water SA. 6, 196-203. Sieburth, J. McN.& Jensen, A. (1969). Studies on algal substances in the sea. II. The formation of Gelbstoff (humic material) by exudates of Phaeophyta. ar. Exp. Mar. Biol. Ecol., 3,275-89. Sieburth, J. McN.& Jensen, A. (1970). Production and transformation of extracellular organic matter from littoral algae: a resume. In Symposium on Organic Matter in Natural Waters, ed D. W. Hood, University of Alaska, Fairbanks, pp. 203-23. Spotte, S. (1979). Seawater Aquariums." The Captive Environment, Wiley, New York, pp. 50-4. Spotte, S. & Adams, G. (1982). Effect of two polymeric resins on total organic carbon (TOC) in recirculated seawater. Aquaculture, 29,159-64. Suffet, I. H. (1980). An evaluation of activated carbon for drinking water treatment: a National Academy of Science report. J. Am. Water Works Assoc., 72, 41-50. US EPA. (1973). Process design manual for carbon adsorption. PB-227 157, NTIS, Springfield, Virginia. Williams, P. J. LeB. (1966). The wet oxidation of organic matter in seawater. Limnol. Oceanogr., 12,292-6. Ying, W-C. & Weber, W. J. Jr. (1979). Bio-physicochemical adsorption model systems for wastewater treatment. J. WaterPollut. Contr. Fed., 51, 2661-77. Yu, M-L. & Perlmutter, A. (1970). Growth inhibiting factors in the zebrafish, Brachydanio rerio and the blue gourami, Trichogaster m'choptems. Growth, 34, 153-75.