UNI-Aqua

Recycling Technology

By Dr. Bent Urup, UNI-Aqua A/S, October 2004

Contents:
  1. Definition of recycling
  2. Water treatment concept
  3. Introduction to recirculation chemistry

1) Definition of recycling

In general, there is often confusion about what is meant by recycling and what is meant by reuse.

Recycling is when the water quality is in control of the water treatment system, not by the inlet water. In recycling systems ammonia is transferred into nitrate and normally less than 1% of the water has to be replaced with new water per cycle.

Moderate recycling only requires a mechanical filtration, CO2 removal, Oxygenation and biofilter for degradation of dissolved organic matter and nitrification. Which means that ammonia is transformed into nitrate, which is then diluted out of the system. Depending on fish species, 50-200 mg nitrate (N) (885mg NO3-) is acceptable.

High levels of recirculation will require a denitrification filter and potentially a means to filter phosphorus as well. In the denitrification filter, which is an anaerobic filter, the nitrate is transferred into free nitrogen. If we include denitrification filters, we can reach recycling levels where we need less than 0.1% new water and where the water leaving the system can potentially be reduced to the water content in the sludge, plus what leaves through evaporation.

2) Water treatment concept

Leaving the tanks, the water will undergo mechanical filtration to remove as much organic matter as possible, then CO2 will be removed and ammonia transferred into nitrate. Finally, Oxygen will be added before the water re-enters the tanks. UV systems are often applied to control the pathogen situation.
Depending on technology, fish species and chemical parameters required, either a single loop or a multi loop system is applied.

In an old style single loop system, all the water is mechanically filtered, directed through the biofilter then through CO2 stripping and further through oxygenation before the water returns to the fish tanks.

In the multi loop system (see figure 1) all the water is mechanically filtered, then the flow through CO2 stripping, biofilter and potentially denitrification filter and phosphorus removal are individually dimensioned/optimised to match the required water chemical specifications.






Figure 1. Illustration of a multi loop system.


3) Introduction to recycling chemistry

Food and energy conversion in flatfish species as an example (Figure 2):



Figure 2. Mass flow for flatfish in recirculation.

The values are of a general nature, as the actual values will always depend on a number of parameters related to the actual production situation.

The point is that whatever proportion of the feed that is not absorbed by the fish will be released, and somehow has to be removed by the water treatment system.

The key chemical components in recirculation are nitrogen, carbon dioxide, oxygen and phosphorus.

Nitrogen
Nitrogen will mainly be excreted by the fish as ammonia. Approx. 80% of the ammonia excreted by the animals will be excreted over the gills, while the rest will be excreted in the faeces. The ammonia excreted over the gills will be unionised- NH3, but due to the pH and the high pKa value of the NH3 - NH4+ buffer system, the majority will immediately be converted to NH4+, which is not nearly as toxic to the fish, as it does not pass back into the animals across the gill epithelia.

NH3 is quite toxic and for the majority of fish species, the level of NH3 should not be above 0.02 mg/litre under normal production conditions. If the levels are very stable, levels twice as high can be accepted as peak values. Further increases will cause reduced growth of the fish.

The problem with ammonia is more serious in seawater because of the high pH, see fig. below. Any sudden increase in pH has to be avoided - pH has to be maintained at a very stable level.


FIGURE 3. The NH3/NH4+ equilibrium in water.

The NH3 - NH4+ equilibrium is however not only dependant on the pH, the salinity also has some influence as well. Depending on the source, you will find small differences in measured amounts.

Recirculation facilities with poor biofiltration (nitrification) performance, permanently operate with low pH levels to avoid the consequence of high ammonia levels. High ammonia levels will alternatively cause poor feeding rate, poor feed conversion and potentially mortality. Reducing the pH is though not a suitable way to control the ammonia situation. The low pH is normally not very optimal for the fish, further the biofilter will function poorly and finally it is a very risky strategy. Farms applying this strategy have unexpectedly lost large amounts of fish do to sharp increases in pH level caused by accident, typically addition of more base than needed.

Carbon Dioxide
The second most important waste product is carbon dioxide. It is excreted over the gills. In addition to that further degradation of feed and faeces will also produce free CO2.

The fish use oxygen to oxidise fats, sugars and proteins. The carbon chains are broken to free energy and the carbon atoms are then released as CO2. As a total breakdown- energy derived from fat will produce approx. 0.71 mole of CO2 per mole of O2 used. When proteins are the energy source 0.8 moles of CO2 will be produced per mole of O2; whereas using glucose as an energy source there will be 1 mole of CO2 produced for each mole of O2.

In seawater, we have to pay special attention to the carbon dioxide because of the pH dependant chemical equilibrium with HCO3- and CO32-.



Figure 4. The carbon dioxide system in water.

In seawater the majority of CO2 will be transformed to HCO3- (less so in freshwater due to its lower pH), which is not as big of a problem for the fish as is the CO2, although it still seems to influence the capacity of the blood to transport the CO2 from the tissue to the gills. Clearly HCO3- must not be allowed to build up in system.

The equilibrium between CO2 and HCO3- in seawater gives some benefits but also some disadvantages. The benefit is that in a pump-through system the carbon dioxide will be converted to HCO3- which is less harmful to the fish. The disadvantage is that it gets more difficult to get out of the water again in a recycled system. This means if we don't have an effective system for removing carbon dioxide, we will have a slow build up of CO2/HCO3- to unacceptable levels. Optimally, the recirculation system should keep the levels of CO2 below 10-20 mg/l. This is clearly one of the major difficulties in marine recirculation technologies, as higher levels will cause reduction in growth.
Aqua-Partners ApS/UNI-Aqua A/S have developed a system where CO2 levels can be maintained below 10 mg/litre in seawater (also in freshwater), where recycled plants in general, operate with levels between 60 and 100 mg CO2/l.

High CO2 levels in freshwater systems should also be kept below 20 mg and should never exceed 30 mg; as growth will be reduced and feed conversion poor. For salmon smolt produced in CO2 rich water, it seems the growth is considerably lower even when the fish have been transferred to the cages.

Phosphorus
The production of phosphorus will only at very high recycling levels be a problem to the fish, if using foam separators, it can even have some benefits in supporting the foam creation. Too high levels will have some impact on CO2 removal.
If needed, a phosphorus filter is a relatively simple and well-proven piece of technology.

BOD5
The biological oxygen demand (BOD5) is a very important factor and one of the reasons why it is important to effectively remove particulate matter in the mechanical filter. From figure 2 it can be seen that by removing particulate matter, we also remove nitrogen and phosphorus.

If we don't remove the particulate matter, it alternatively has to be broken down by biological means in the production water, resulting in the consumption of oxygen and production of carbon dioxide, which we then have to add/remove. It is important to notice that the level of BOD5 in the biological filter has to be relatively low before the filter starts working at converting ammonia products. The simplest way and the first step in making the bio filter work effectively, is by having effective mechanical filtration.
In seawater, due to its high pH and consequently high proportion of unionised ammonia, it is necessary for the nitrification to work without interruption. Therefore, a biofilter structure normally applied in freshwater, can not be used for Seawater. Opposite a biofilter designed for seawater will work very well with freshwater.

Oxygen
The fish will use oxygen for oxidizing their food; see above under carbon dioxide. We can add oxygen to the animals by adding new water with a natural oxygen content. Further, we can aerate the water thereby transferring oxygen from the atmosphere to the production water. Finally we can also use pure oxygen, which can be introduced in several ways.

Super-saturation of the inlet water to the tanks is often used. This is often a suitable method, however in the tanks the water should only be slightly super-saturated with oxygen, as too high levels (typical levels above 110% -120% oxygen saturation) will reduce growth rates. In cases where CO2 levels are high, oxygen super-saturation is often used to improve growth results, the system will then operate with too high carbon dioxide/bicarbonate levels- as well as O2 levels as these two parameters interact. This is though symptom treatment. It will give better results and less stress to the fish, if both parameters are under control, and managed within an optimal range.
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