Controlling phosphorous discharged from municipal and industrial wastewater treatment plants is a key factor in preventing eutrophication of surface waters. Phosphorous is one of the major nutrients contributing in the increased eutrophication of lakes and natural waters. Its presence causes many water quality problems including increased purification costs, decreased recreational and conservation value of an impoundments, loss of livestock and the possible lethal effect of algal toxins on drinking water.

Phosphorous in wastewater

Municipal wastewaters may contain from 5 to 20 mg/l of total phosphorous, of which 1-5 mg/l is organic and the rest in inorganic. The individual contribution tend to increase, because phosphorous is one of the main constituent of synthetic detergents. The individual phosphorous contribution varies between 0.65 and 4.80 g/inhabitant per day with an average of about 2.18 g. The usual forms of phosphorous found in aqueous solutions include:

• Orthophosphates: available for biological metabolism without further breakdown
• Polyphosphates: molecules with 2 or more phosphorous atoms, oxygen and in some cases hydrogen atoms combine in a complex molecule. Usually polyphosphates undergo hydrolysis and revert to the orthophosphate forms. This process is usually quite slow.

Normally secondary treatment can only remove 1-2 mg/l, so a large excess of phosphorous is discharged in the final effluent, causing eutrophication in surface waters. New legislation requires a maximum concentration of P discharges into sensitive water of 2 mg/l.

Phosphorous removal processes

The removal of phosphorous from wastewater involves the incorporation of phosphate into TSS and the subsequent removal from these solids. Phosphorous can be incorporated into either biological solids (e.g. micro organisms) or chemical precipitates.

Phosphate precipitation

Chemical precipitation is used to remove the inorganic forms of phosphate by the addition of a coagulant and a mixing of wastewater and coagulant. The multivalent metal ions most commonly used are calcium , aluminium and iron .

Calcium:

it is usually added in the form of lime Ca(OH) 2 . It reacts with the natural alkalinity in the wastewater to produce calcium carbonate, which is primarily responsible for enhancing SS removal.

Ca(HCO 3 ) 2 + Ca(OH) 2 --> 2CaCO 3 ?+ 2H 2 O

As the pH value of the wastewater increases beyond about 10, excess calcium ions will then react with the phosphate, to precipitate in hydroxylapatite:

10 Ca 2+ + 6 PO 4 3- + 2 OH - ? Ca 10 (PO 4 )*6(OH) 2 ?

Because the reaction is between the lime and the alkalinity of the wastewater, the quantity required will be, in general, independent of the amount of phosphate present. It will depend primarily on the alkalinity of the wastewater. The lime dose required can be approximated at 1.5 times the alkalinity as CaCO 3 . Neutralisation may be required to reduce pH before subsequent treatment or disposal. Recarbonation with carbon dioxide (CO 2 ) is used to lower the pH value.

Aluminium and Iron:

Alum or hydrated aluminium sulphate is widely used precipitating phosphates and aluminium phosphates (AlPO 4 ). The basic reaction is:

Al 3+ + H n PO 4 3-n --> AlPO 4 + nH +

This reaction is deceptively simple and must be considered in light of the many competing reactions and their associated equilibrium constants and the effects of alkalinity, pH, trace elements found in wastewater. The dosage rate required is a function of the phosphorous removal required. The efficiency of coagulation falls as the concentration of phosphorous decreases. In practice, an 80-90% removal rate is achieved at coagulant dosage rates between 50 and 200 mg/l. Dosages are generally established on the basis of bench-scale tests and occasionally by full-scale tests, especially if polymers are used. Aluminium coagulants can adversely affect the microbial population in activated sludge, especially protozoa and rotifers, at dosage rates higher than 150 mg/l. However this does not affect much either BOD or TSS removal, as the clarification function of protozoa and rotifers is largely compensated by the enhanced removal of SS by chemical precipitation.

Ferric chloride or sulphate and ferrous sulphate also know as copperas, are all widely used for phosphorous removal, although the actual reactions are not fully understood. The basic reaction is:

Fe 3+ + H n PO 4 3-n --> FePO 4 + nH +

Ferric ions combine to form ferric phosphate. They react slowly with the natural alkalinity and so a coagulant aid, such as lime, is normally add to raise the pH in order to enhance the coagulation .

Strategies

The main phosphate removal processes are (see picture below):

1. Treatment of raw/primary wastewater

2. Treatment of final effluent of biological plants (postprecipitation)

3. Treatment contemporary to the secondary biologic reaction (co-precipitation).

The first process is included in the general category of chemical precipitation processes. Phosphorous is removed with 90% efficiency and the final P concentration is lower than 0.5 mg/l. The chemical dosage for P removal is the same as the dosage needed for BOD and SS removal, which uses the main part of these chemicals. As mentioned above lime consumption is dependent on the alkalinity of the wastewater: only 10% of the lime fed is used in the phosphorous removal reaction. The remaining amount reacts with water alkalinity, with softening. To determine the lime quantity needed it is possible to use diagrams: i.e. the lime used to reach ph 11 is 2-2.5 times water alkalinity.

The postprecipitation is a standard treatment of a secondary effluent, usually using only metallic reagents. It is the process that gives the highest efficiency in phosphorous removal. Efficiency can reach 95%, and P concentration in the effluent can be lower than 0.5 mg/l. Postprecipitation gives also a good removal of the SS that escape the final sedimentation of the secondary process. Its advantage is also to guarantee purification efficiency at a certain extent even if the biological process is not efficient for some reason. The chemical action is stronger, since the previous biologic treatment transforms part of the organic phosphates in orthophosphates. Disadvantages are high costs for the treatment plant (big ponds and mixing devices) and sometimes a too dilute effluent. Using ferric salts there is also the risk of having some iron in the effluent, with residual coloration. The metallic ions dosage is about 1.5-2.5 ions for every phosphorus ion (on average about 10-30 g/mc of water).

The coprecipitation process is particularly suitable for active sludge plants, where the chemicals are fed directly in the aeration tank or before it. The continuous sludge recirculation, together with the coagulation-flocculation and adsorption process due to active sludge, allows a reduction in chemical consumption. Moreover the costs for the plant are lower, since there is no need for big postprecipitation ponds. In this process the chemical added are only iron and aluminium, lime is added only for pH correction. Lower costs and more simplicity are contrasted by a phosphorous removal efficiency lower than with postprecipitation (below 85%). The phosphorous concentration in the final effluent is about 1 mg/l. Another disadvantage is that biological and chemical sludge are mixed, so they cannot be used separately in next stages. Mixed sludges need bigger sedimentation tanks than activated sludge.

Biological processes

Over the past 20 years, several biological suspended growth process configurations have been used to accomplish biological phosphorous removal. The most important are shown in the following picture.

The principal advantages of biological phosphorous removal are reduced chemical costs and less sludge production as compared to chemical precipitation.

In the biological removal of phosphorous, the phosphorous in the influent wastewater is incorporated into cell biomass, which is subsequently removed from the process as a result of sludge wasting. The reactor configuration provides the P accumulating organisms (PAO) with a competitive advantage over other bacteria. So PAO are encouraged to grow and consume phosphorous. The reactor configuration in comprised of an anaerobic tank and an activated sludge activated tank. The retention time in the anaerobic tank is about 0.50 to 1.00 hours and its contents are mixed to provide contact with the return activated sludge and influent wastewater.

In the anaerobic zone : Under anaerobic conditions, PAO assimilate fermentation products (i.e. volatile fatty acids) into storage products within the cells with the concomitant release of phosphorous from stored polyphosphates. Acetate is produced by fermentation of bsCOD, which is dissolved degradable organic material that can be easily assimilated by the biomass. Using energy available from stored polyphosphates, the PAO assimilate acetate and produce intracellular polyhydroxybutyrate (PHB) storage products. Concurrent with the acetate uptake is the release of orthophosphates, as well as magnesium , potassium , calcium cations. The PHB content in the PAO increases as the polyphosphate decreases.

In the aerobic zone : energy is produced by the oxidation of storage products and polyphosphate storage within the cell increases. Stored PHB is metabolized, providing energy from oxidation and carbon for new cell growth. Some glycogen is produced from PHB metabolism. The energy released from PHB oxidation is used to form polyphosphate bonds in cell storage. The soluble orthophosphate is removed from solution and incorporated into polyphosphates within the bacterial cell. PHB utilisation also enhances cell growth and this new biomass with high polyphosphate storage accounts for phosphorous removal. As a portion of the biomass is wasted, the stored phosphorous is removed from the biotreatment reactor for ultimate disposal with the waste sludge.

The amount of phosphorous removed by biological storage can be estimated from the amount of bsCOD that is available in the wastewater influent. Better performance for BPR systems is achieved when bsCOD acetate is available at a steady rate.

There are also commercially available Phosphorus removal filters such as:

>> Blue PRO

>> Imbrium Systems Sorbtive Media

Interesting paper on Chemical Phosphorus Removal

Here is another very interesting paper on Phosphorus removal.

Compiled by Rami E. Kremesti M.Sc.

Sources:

§ ‘ Wastewater Engineering', Metcalf & Eddy, International Edition, 2003

§ ‘Water technology', N.F. Gray, Elsevier, 2005

§ ‘Depurazione acque', Luigi Masotti, Calderini, 2005