358 CouquiaudActivated Carbon—Activated carbon isamong the most effective materials for the physicalabsorption <strong>of</strong> organic carbon (Spotte, 1991).They are classified <strong>in</strong> the paragraph on mechanicalfiltration because they function on a physicalpr<strong>in</strong>ciple <strong>of</strong> absorption. These filters are made <strong>of</strong>absorbents manufactured from a number <strong>of</strong> carbonbasedmaterials. They typically have a 0.5 to 1 µmfiltration capability, mak<strong>in</strong>g it helpful for particulatefiltration. Activated carbon commonly is usedfor dechlor<strong>in</strong>ation, for reduc<strong>in</strong>g soluble materialssuch as Dissolved Organic Carbon (DOC)—chloram<strong>in</strong>esissued from chlor<strong>in</strong>ation—and to preventthe accumulation <strong>of</strong> total organic carbon (TOC)precursors <strong>of</strong> trihalomethanes (THM; mutagenicand carc<strong>in</strong>ogenic compounds present as traceconcentrations <strong>in</strong> chlor<strong>in</strong>ated water and ozonatedseawater) <strong>in</strong> closed systems (Anonymous, 1999;Spotte, 1991). It can be <strong>in</strong>stalled on a side-streamafter mechanical filtration <strong>in</strong> comb<strong>in</strong>ation withvarious oxidation systems. Activated carbon doesnot have a long life span and is quite expensive tochange. The disposed material has to be treated ashazardous waste (Spotte, 1991).Chemical PurificationRidgway (1972) calculated that a dolph<strong>in</strong>, weigh<strong>in</strong>g136 kg and eat<strong>in</strong>g 6.6 kg <strong>of</strong> fish, passes over4 l <strong>of</strong> ur<strong>in</strong>e and 1.4 kg <strong>of</strong> faeces per day. Themajority <strong>of</strong> this waste matter is soluble, and highlevels <strong>of</strong> organic nitrogen make a very good culturemedium for bacterial and fungal growth. Itis important to remove these matters by elim<strong>in</strong>at<strong>in</strong>gthe water through an open circuit or throughthe use <strong>of</strong> oxidation <strong>in</strong> a closed system (Manton,1986). Chemical reactions also are related to temperature.The development <strong>of</strong> bacteria is acceleratedby high temperature.The objective <strong>of</strong> water sterilisation is to placethe agent <strong>in</strong> contact with microorganisms by themost efficient means. Two methods are used:(1) po<strong>in</strong>t-contact sterilisation (e.g., ozonation,UV irradiation) or (2) bulk-fluid (e.g., chlor<strong>in</strong>ation)(Spotte, 1991). Chemical purification also<strong>in</strong>cludes catalysts such as copper and silver. Themost widely distributed systems used are chlor<strong>in</strong>ationand ozonation. Chlor<strong>in</strong>ation still is used bya majority <strong>of</strong> facilities, but ozonation has becomequite popular. Chlor<strong>in</strong>ation as a s<strong>in</strong>gle choice is<strong>in</strong> decl<strong>in</strong>e.Silver and Copper Catalysts—Metal ions, suchas silver and copper, used <strong>in</strong> conjunction withchlor<strong>in</strong>ation, are efficient for ma<strong>in</strong>ta<strong>in</strong><strong>in</strong>g goodwater clarity, remov<strong>in</strong>g bacteria, and control<strong>in</strong>galgae; however, copper toxicity has been reported<strong>in</strong> mar<strong>in</strong>e mammals (Boness, 1996; McDevitt,1986) and copper might accumulate <strong>in</strong> the liver(Ford, 1997). Its use will therefore be avoided.Chlor<strong>in</strong>ation—Chlor<strong>in</strong>e is one <strong>of</strong> the mostpopular chemical agents used for the elim<strong>in</strong>ation<strong>of</strong> microorganisms and algae (Faulk, 1990); however,it is a difficult process and can give rise to anumber <strong>of</strong> problems (Boness, 1996; van der Toorn,1987). Injudicious use <strong>of</strong> such chemicals canbe more life-threaten<strong>in</strong>g than the organisms andexcreta they control (Geraci, 1986). As opposed toozone, chlor<strong>in</strong>e generally is used as an oxidis<strong>in</strong>gagent <strong>in</strong> the bulk-fluid and has a prolonged time<strong>of</strong> action. Chlor<strong>in</strong>e-based products are <strong>in</strong>expensive,possess strong antimicrobial properties, andare easy to store and <strong>in</strong>ject; however, they presentimportant disadvantages <strong>in</strong> that they form productswith lower oxidation potential—the chloram<strong>in</strong>es—aswell as mutagenic and carc<strong>in</strong>ogenicbyproducts (Spotte, 1991). Therefore, byproducts<strong>of</strong> the transformed chlor<strong>in</strong>e are hazardous if notremoved by chemical processes or frequent waterrenewal.Chlor<strong>in</strong>e is available as liquified gas (under pressureand referred to as liquid chlor<strong>in</strong>e) and as solutions<strong>of</strong> chlor<strong>in</strong>e compounds such as sodium hypochlorite(Manton, 1986); however, as Geraci (1986)stated, chlor<strong>in</strong>e as sodium hypochlorite is perhapsthe most commonly misused chemical treatment.When chlor<strong>in</strong>e gas (Cl2) or sodium hypochloriteis mixed with water, it is transformed <strong>in</strong>tohypochlorous acid (HOCl), which is an excellentoxidiser (Faulk, 1990; Manton, 1986; Spotte,1991). For optimal oxidation, pH has to be ma<strong>in</strong>ta<strong>in</strong>edbetween 7.5 and 7.6. At higher pH levels,the concentration <strong>of</strong> hypochlorous acid, the activeagent, will drop, therefore reduc<strong>in</strong>g its sterilisationcapacities. Hypochlorous acid is highly unstable,however, as it breaks down with sunlight (Faulk1990). Free chlor<strong>in</strong>e is the amount <strong>of</strong> hypochlorousacid and hypochlorite ions (OCl-) free andavailable to react. Hypochlorous acid reacts withammonia from ur<strong>in</strong>ary waste to form differentchloram<strong>in</strong>es (monochloram<strong>in</strong>e and subsequentlydichloram<strong>in</strong>e and nitrogen trichloride). They persistlonger than free chlor<strong>in</strong>e, but they possesslower oxidis<strong>in</strong>g potential (Spotte, 1991).Pool water is tested <strong>in</strong> dolph<strong>in</strong>aria for free andtotal chlor<strong>in</strong>e. The survey showed that a safe rangeis below 0.2 ppm for free chlor<strong>in</strong>e and 0.5 ppmfor total chlor<strong>in</strong>e (comb<strong>in</strong>ed residual chlor<strong>in</strong>e).Saltwater test kits for chlor<strong>in</strong>e and chloram<strong>in</strong>escan be used. Most <strong>of</strong> them give free and totalchlor<strong>in</strong>e read<strong>in</strong>gs. Faulk (1990) recommends todel<strong>in</strong>eate chloram<strong>in</strong>es as well. <strong>Survey</strong>ed facilitiesperform these tests two to three times per day.Chlor<strong>in</strong>e is a good bactericide; however, manyprotozoans, yeasts, cysts, and viruses are resistant(Boness, 1996). Sk<strong>in</strong> <strong>in</strong>fections are quite common <strong>in</strong>chlor<strong>in</strong>ated water. It can be the result <strong>of</strong> the destruction<strong>of</strong> beneficial micr<strong>of</strong>lora and the <strong>in</strong>activation <strong>of</strong>
6. Life Support Systems 359antimicrobial substances secreted by the sk<strong>in</strong> (Geraciet al., 1986; van der Toorn, 1987). It potentially can<strong>in</strong>terfere with the dolph<strong>in</strong>’s ability to detect pheromonesproduced by other dolph<strong>in</strong>s for social andsexual <strong>in</strong>teractions (Herman & Tavolga, 1980; vander Toorn, 1987). Free chlor<strong>in</strong>e used <strong>in</strong> the presence<strong>of</strong> humic and fulvic acids (e.g., natural dissolvedorganic carbon [DOC] or substances derived fromhumus) or some algae can produce carc<strong>in</strong>ogenic trialomethanes(THM) (Boness, 1996; Spotte, 1991).<strong>Cetaceans</strong> <strong>in</strong>gest<strong>in</strong>g a m<strong>in</strong>imal amount <strong>of</strong> pool waterare at m<strong>in</strong>imal risks, however, if any at all (Spotte,1991). Although their oxidation potential is lower,chloram<strong>in</strong>es are capable <strong>of</strong> reduc<strong>in</strong>g concentrations<strong>of</strong> THM substantially (Spotte, 1991).Another chlor<strong>in</strong>e-based oxidant is chlor<strong>in</strong>edioxide (ClO2), which is mixed on-site and presentsthe advantage <strong>of</strong> not form<strong>in</strong>g chloram<strong>in</strong>esdirectly, does not yield THM, does not react withbromide, and has comparable sterilis<strong>in</strong>g potentialat lower dosages and contact times. It is sensitiveto temperature, pressure, and light, however,which means that it has to be generated on sitelike ozone. It also is more expensive than otherchlor<strong>in</strong>e-based oxidants.Seawater and artificial seawater conta<strong>in</strong> bromide.Chlor<strong>in</strong>ation <strong>of</strong> these waters results <strong>in</strong> variouselements together called active brom<strong>in</strong>e thatconvert later <strong>in</strong>to bromate and potentially brom<strong>in</strong>atedTHM. Moreover, the presence <strong>of</strong> bromidereacts with chlor<strong>in</strong>e and <strong>in</strong>creases chlor<strong>in</strong>edemand (Spotte, 1991).Chlor<strong>in</strong>e always will be added to the water afterthe mechanical filtration through a high-quality<strong>in</strong>jection system and be properly mixed. Manuallyadd<strong>in</strong>g any type <strong>of</strong> chlor<strong>in</strong>e is unsafe for both techniciansand animals, and it does not properly distributethe chemical <strong>in</strong> the pool (Boness, 1996).If dolph<strong>in</strong>s are seen frequently with closed eyes,show signs <strong>of</strong> eye irritation, occasionally cough,or if the water smells <strong>of</strong> chlor<strong>in</strong>e, the chlor<strong>in</strong>ationsystem probably is unbalanced. Action shouldbe taken immediately to correct the problem asit can damage the animal’s sk<strong>in</strong> and eyes. Properventilation above and around the pools is crucial(Amund<strong>in</strong>, 1986; survey).Chlor<strong>in</strong>e also can be used <strong>in</strong> very small amounts(close to dr<strong>in</strong>k<strong>in</strong>g water) <strong>in</strong> an open system or <strong>in</strong>conjunction with ozonation. Chlor<strong>in</strong>ation is <strong>in</strong>compatiblewith biological purification, however.Ozonation—Ozone (O3) is a po<strong>in</strong>t-contact sterilis<strong>in</strong>gagent that is also used for water discoloration.It also can have some effect <strong>in</strong> remov<strong>in</strong>gturbidity. Ozone is an excellent oxidis<strong>in</strong>g agentand bactericide. It also is effective <strong>in</strong> oxidis<strong>in</strong>gorganic matter, iron, and manganese. It is, therefore,a convenient and efficient sterilis<strong>in</strong>g agentfor mar<strong>in</strong>e mammal pools. It produces no taste orodour <strong>in</strong> the water. Ozone destroys bacteria andmold; elim<strong>in</strong>ates spores, yeast, and fungus; andpossibly <strong>in</strong>activates viruses and cysts. Its effectivenessdecreases at higher densities <strong>of</strong> organisms(van der Toorn, 1987). S<strong>in</strong>ce ozonation doesnot leave a dis<strong>in</strong>fectant agent <strong>in</strong> the water, it doesnot have a long-last<strong>in</strong>g effect like chlor<strong>in</strong>e, hencerequir<strong>in</strong>g a high water turnover.Ozone is a highly reactive form <strong>of</strong> oxygen andcan be produced by send<strong>in</strong>g a high voltage electricaldischarge through air or oxygen (such aswhat occurs <strong>in</strong> a lightn<strong>in</strong>g storm). Some degree<strong>of</strong> ozone also can be produced by certa<strong>in</strong> types<strong>of</strong> UV lamps. As a gas, ozone is unstable and hasa very short life, so it must be generated at thepo<strong>in</strong>t <strong>of</strong> use. UV ozone generators are relativelysimple and economical but are limited <strong>in</strong> outputcapacity. For larger volume treatment, a Coronadischarge ozone generator is used. Air or concentratedoxygen is used to produce ozone on-site. ACorona discharge system uses very high voltage(5,000 to 14,000V) to split oxygen molecules,which will bond with other oxygen molecules andcreate ozone. Ozone is mixed with water <strong>in</strong> a reactiontank where the oxidation process occurs. Theundissolved ozone/air mixture must be collected<strong>in</strong> the reaction tank and destroyed; otherwise, thisdangerous gas will be entra<strong>in</strong>ed <strong>in</strong> the water flowand released, for example, <strong>in</strong>to the atmosphere,at the pool water surface (Anonymous, 1997;Boness, 1996). Moisture <strong>in</strong> the gas stream shouldbe reduced to a m<strong>in</strong>imum as it can cause a seriousdrop <strong>in</strong> ozone production and the formation <strong>of</strong>nitric acid (Anonymous, 1997; Krajniak, 1988).The concentration (C, <strong>in</strong> mg/l or ppm) <strong>of</strong> dissolvedozone multiplied by the time (T, <strong>in</strong> m<strong>in</strong>utes) <strong>of</strong> contactbetween the dissolved ozone and the contam<strong>in</strong>ants <strong>in</strong>the water provides a “CT value.” Ozone, as a primarysterilis<strong>in</strong>g method, achieves adequate sterilisationwith a CT <strong>of</strong> 1.6 (e.g., 0.4 mg/l <strong>of</strong> dissolved ozonema<strong>in</strong>ta<strong>in</strong>ed for 4 m<strong>in</strong> equals a CT <strong>of</strong> 1.6) or greater.If the concentration is too low or the contact time to<strong>of</strong>ast, sterilisation will not be optimal. High turbidity,cold temperatures, and high pH decrease the sterilisationcapacity as well. Guidel<strong>in</strong>es <strong>of</strong> CT values for theefficient destruction <strong>of</strong> microorganisms can be found<strong>in</strong> the Guidance Manual for Compliance with theFiltration and Dis<strong>in</strong>fection Requirements for PublicWater Systems Us<strong>in</strong>g Surface Water Supplies, published<strong>in</strong> 1989 by the USA Environmental ProtectionAgency <strong>in</strong> Wash<strong>in</strong>gton, DC. Countries, such asFrance and Canada, have adopted the same standards(Anonymous, 1997). The production <strong>of</strong> ozoneusually is expressed <strong>in</strong> g/l. In relation to the variableload and pollution <strong>in</strong> the water, the ozone quantityis controlled and adjusted by a Redox (Reduction/Oxidation) measur<strong>in</strong>g apparatus. An ozone detectorshould be <strong>in</strong>stalled <strong>in</strong> the direct vic<strong>in</strong>ity <strong>of</strong> the ozone
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