Chemical Phosphorus Removal
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Chemical phosphorus removal is a wastewater treatment method, where phosphorus is removed using salts of
aluminum Aluminium (aluminum in American and Canadian English) is a chemical element with the symbol Al and atomic number 13. Aluminium has a density lower than those of other common metals, at approximately one third that of steel. It has ...
(e.g.
alum An alum () is a type of chemical compound, usually a hydrated double salt, double sulfate salt (chemistry), salt of aluminium with the general chemical formula, formula , where is a valence (chemistry), monovalent cation such as potassium or a ...
or polyaluminum chloride),
iron Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...
(e.g.
ferric chloride Iron(III) chloride is the inorganic compound with the formula . Also called ferric chloride, it is a common compound of iron in the +3 oxidation state. The anhydrous compound is a crystalline solid with a melting point of 307.6 °C. The colo ...
), or
calcium Calcium is a chemical element with the symbol Ca and atomic number 20. As an alkaline earth metal, calcium is a reactive metal that forms a dark oxide-nitride layer when exposed to air. Its physical and chemical properties are most similar to ...
(e.g. lime).
Phosphate In chemistry, a phosphate is an anion, salt, functional group or ester derived from a phosphoric acid. It most commonly means orthophosphate, a derivative of orthophosphoric acid . The phosphate or orthophosphate ion is derived from phospho ...
forms precipitates with the metal ions and is removed together with the sludge in the separation unit (
sedimentation tank Sedimentation is a physical water treatment process using gravity to remove suspended solids from water. Solid particles entrained by the turbulence of moving water may be removed naturally by sedimentation in the still water of lakes and oceans. ...
, flotation tank, etc.).


Aluminum sulfate treatment to reduce phosphorus content of lakes

One method of
eutrophication Eutrophication is the process by which an entire body of water, or parts of it, becomes progressively enriched with minerals and nutrients, particularly nitrogen and phosphorus. It has also been defined as "nutrient-induced increase in phytopla ...
remediation is the application of
aluminum sulfate Aluminium sulfate is a salt with the formula Al2 (SO4)3. It is soluble in water and is mainly used as a coagulating agent (promoting particle collision by neutralizing charge) in the purification of drinking water and wastewater treatment plant ...
, a salt commonly used in the coagulation process of drinking
water treatment Water treatment is any process that improves the Water quality, quality of water to make it appropriate for a specific end-use. The end use may be drinking water, drinking, industrial water supply, irrigation, river flow maintenance, water recrea ...
. Aluminum sulfate, or “alum” as it is commonly referred, has been found to be an effective lake management tool by reducing the
phosphorus Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
load. Alum was first applied in 1968 to a lake in Sweden. Its first application to an American lake followed in 1970. Today, alum has been utilized with improved effectiveness and understanding. In a large scale study, 114 lakes were monitored for the effectiveness of alum at phosphorus reduction. Across all lakes, alum effectively reduced the phosphorus for 11 years. While there was variety in the longevity, (21 years in deep lakes and 5.7 years in shallow lakes), the results express the effectiveness of alum at controlling phosphorus within lakes.


Mechanism

Alum treatment begins with the addition of aluminum sulfate salt to a water body. Once added, the salt dissolves and dissociates, introducing Al(III) ions to the water. The aluminum ions participate in a series of
hydrolysis Hydrolysis (; ) is any chemical reaction in which a molecule of water breaks one or more chemical bonds. The term is used broadly for substitution reaction, substitution, elimination reaction, elimination, and solvation reactions in which water ...
reactions, forming different aluminum species across pH ranges. As more aluminum sulfate is added, water pH decreases. At higher pH, the soluble species Al(OH)4 is present. In neutral pH ranges (6-8), the insoluble
aluminum hydroxide Aluminium hydroxide, Al(OH)3, is found in nature as the mineral gibbsite (also known as hydrargillite) and its three much rarer polymorphs: bayerite, doyleite, and nordstrandite. Aluminium hydroxide is amphoteric, i.e., it has both basic and ...
(Al(OH)3) occurs. As pH decreases further, the Al(III) ion remains present. Maintaining optimal pH is important for the removal of phosphorus from water. Phosphorus is most effectively removed at the neutral pH range, when the insoluble aluminum hydroxide is present. This hydroxide functions as a
Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...
, creating a
flocculation Flocculation, in the field of chemistry, is a process by which colloidal particles come out of suspension to sediment under the form of floc or flake, either spontaneously or due to the addition of a clarifying agent. The action differs from pr ...
environment similar to conventional wastewater treatment. The insoluble Al(OH)3 floc
adsorbs Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a Surface science, surface. This process creates a film of the ''adsorbate'' on the surface of the ''adsorbent''. This process differs from absorpti ...
phosphorus, as well as other species, and removes them from the water column. As floc adsorption continues, the floc becomes larger, eventually settling to the bottom of the
water column A water column is a conceptual column of water from the surface of a sea, river or lake to the bottom sediment.Munson, B.H., Axler, R., Hagley C., Host G., Merrick G., Richards C. (2004).Glossary. ''Water on the Web''. University of Minnesota-D ...
in the sediment. The resulting aluminum hydroxide layer covering the lake bottom additionally blocks the diffusion of phosphorus from sediment into the water column, further regulating internally loaded phosphorus.


Implementation

For most alum treatments, aluminum sulfate salt is applied to substrate at the lake's bottom, within the
hypolimnion The hypolimnion or under lake is the dense, bottom layer of water in a thermally- stratified lake. The word hypolimnion is derived from the Greek "limnos" meaning "lake". It is the layer that lies below the thermocline. Typically the hypolimnio ...
. The alum then reduces phosphorus levels by inactivating the phosphorus released from these lake sediments, thereby controlling phosphorus in the entire water column. This phosphorus supplied from within the lake sediments is known as "internally loaded" phosphorus, as opposed to "externally loaded" phosphorus supplied by sources outside the lake, such as
runoff Runoff, run-off or RUNOFF may refer to: * RUNOFF, the first computer text-formatting program * Runoff or run-off, another name for bleed, printing that lies beyond the edges to which a printed sheet is trimmed * Runoff or run-off, a stock market ...
.Cooke, G. D., Welch, E. B., Martin, A. B., Fulmer, D. G., Hyde, J. B., & Schrieve, G. D. (1993). Effectiveness of Al, Ca, and Fe salts for control of internal phosphorus loading in shallow and deep lakes. ''Hydrobiologia'', ''253''(1), 323-335. Although alum is typically applied to the hypolimnion, reducing phosphorus universally within the lake, it may also be applied to the
epilimnion The epilimnion or surface layer is the top-most layer in a thermally stratified lake. It sits above the deeper metalimnion and hypolimnion. It is typically warmer and has a higher pH and higher dissolved oxygen concentration than the hypolimnion ...
or locally to point sources. This style of alum treatment is similar to the use of alum in conventional water treatment, and is more effective at reducing externally loaded phosphorus than universal application of alum to the hypolimnion. When applied to the epilimnion, boats powered by an
outboard motor An outboard motor is a propulsion system for boats, consisting of a self-contained unit that includes engine, gearbox and propeller or jet drive, designed to be affixed to the outside of the transom. They are the most common motorised method ...
are deployed onto a lake carrying aluminum sulfate. After determining the necessary dosage and location of the application, the aluminum sulfate is added to the surface of the lake near the wake of the outboard motor. This provides sufficient mixing of the aluminum sulfate within the epilimnion. The necessary dosage of alum is determined by a variety of parameters. Changes in pH,
dissolved oxygen Oxygen saturation (symbol SO2) is a relative measure of the concentration of oxygen that is dissolved or carried in a given medium as a proportion of the maximal concentration that can be dissolved in that medium at the given temperature. It ca ...
levels, metal content of lake sediment, and lake size are all important for consideration. Alum dosage is calculated by scientist and engineers to increase the effectiveness.


Limitations

Alum treatment is less effective in deep lakes, as well as lakes with substantial external phosphorus loading. In deep lakes, the inactivation of phosphorus is not spread throughout the entire water column, as it is in shallower lakes due to the localization of aluminum hydroxide to the hypolimnion. Furthermore, externally loaded phosphorus often diffuses slowly downward from the lake surface, limiting its interaction with aluminum hydroxide within the hypolimnion and allowing phosphorus accumulation higher in the water column. Therefore, alum treatment is most effectively applied to shallow lakes with primarily internally loaded phosphorus. One exception is point sources of externally loaded phosphorus, which can be effectively regulated by direct application of aluminum sulfate to the source. Another physical property to be considered is the ability of a lake to withstand mixing in the water column. Lakes with a higher Osgood Index, a parameter used to determine the amount of mixing a that occurs in a lake due to wind, have been found to result in more effective alum treatment. Another parameter is the ratio of the watershed area to the lake surface area. Lakes with lower watershed to lake area ratios experienced greater longevity following treatment. These lakes tend to be correlated with longer residence times and tend to be influenced by internally loaded phosphorus which aids in successful treatment. Regardless of application strategy, repeated alum treatment is often necessary for most lakes every 5 to 15 years. The necessity of repeated treatment requires continuous management and phosphorus monitoring to ensure optimal effectiveness. Biological implications are another important consideration of alum treatment. Treatments increase water clarity, which has been correlated with increased plant growth at greater depths within the lake. Increased plant growth within lakes changes the character of the substrate, which is sometimes a factor in biodiversity. Lakes with
benthic The benthic zone is the ecological region at the lowest level of a body of water such as an ocean, lake, or stream, including the sediment surface and some sub-surface layers. The name comes from ancient Greek, βένθος (bénthos), meaning "t ...
feeding fish such as
carp Carp are various species of oily freshwater fish from the family Cyprinidae, a very large group of fish native to Europe and Asia. While carp is consumed in many parts of the world, they are generally considered an invasive species in parts of ...
tend to have lower success at removing phosphorus. These species forage in lake sediments which disturbs the aluminum hydroxide flocs binding phosphorus to the lake bottom. An additional concern is that aluminum salts can acidify lakes, making them potentially toxic to aquatic organisms. However, the aluminum sulfate dosage used for lake treatment is not often high enough to pose significant toxicity to fish, although declines in algae and invertebrates have been observed in treated lakes. The alum dosage is also insufficient to cause toxicity in humans, and is often similar to alum doses used in conventional drinking water treatment. To reduce negative biological effects, the accepted limit for dissolved aluminum concentrations in a water body is 50 μg Al/L and pH should be restricted to a range of 5.5-9.


References

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External links


Phosphorus removal from wastewater - Lenntech
Water treatment