Copper Stains in Swimming Pools 🤷‍♀️

  

Blue, Green, Black, Gray, and Purple!

photo credit: CDC, 1964, Puerto Rican public health weighing out a measure of copper sulfate, which they would then apply to this waterway in order to control the parasitic population of schistosomes (Snail fever). 

Part of the reason determining the cause of a stain or discolored water in a swimming pool can be challenging is that a metal in water can present as many different colors. There are a lot of factors at play here and as a Pool Pro we must consider them all. In the following, we will touch base on some of the many different metal issues a pool operator may face, but we have chosen to make copper our focus. We chose copper for a couple of reasons, to include: the many variations in appearance, the commonplace use of copper based algaecides, and the frequency of copper as the culprit.

The oldest metal object found in the Middle East consists of copper; it was a tiny awl dating back as far as 5100 B.C. – Stephanie Pappas, Facts About Copper, Live Science

To Skip the Technobabble DO NOT read the Paragraphs in BLUE

hexaaquacopper(II) ions: [Cu(H2O)6]2+ 
A Copper algaecide, such as Copper sulfate pentahydrate, when added can bond with water molecules giving us a brilliant “Copper sulfate Blue”, but crystal clear pool as shown above. This reaction is known as hexaaquacopper.

The Technobabble: Copper sulfate pentahydrate (CuSO4.5H2O) is added to water, it dissolves quickly giving us the crystal clear bluing of hexaaquacopper(II) ions [CuH2O)6]2+ (above). This is simply 6 water molecules (H2O) bonded to a Copper (Cu2+) cation. This is an exothermic reaction meaning that the copper sulfate pentahydrate (CuSO4.5H2O) generates heat as it dissolves. This also means the product, like calcium chloride, will dissolve better in cold water.

copper(II) carbonate hydroxide (Cu2(OH)2CO3), photo: Knockout pools, Texas

If we were to raise the pH or Total Alkalinity in a swimming pool that had copper present, or add a copper algaecide to a swimming pool that already had a high pH and/or Total Alkalinity, we could end up with a cloudy blue pool (above). This is commonly referred to as Copper carbonate. Lowering the pH and/or TA sloooowly should eliminate the appearance of the aftermath of an exploded Smurf, but if you add a large dose of acid quickly… we could turn the pool water Green.

The Technobabble: Increasing the amount of carbonate ions in the solution we would form copper(II) carbonate hydroxide (Cu2(OH)2CO3). This compound is completely insoluble. The copper(II) carbonate hydroxide (Cu2(OH)2CO3) would eventually settle to the pool’s floor, or be removed through filtration. However, this could take quite a bit of time depending on the type of filter (sand, DE, or cartridge).

tetrachlorocuprate(II) ions: Cl4Cu

Adding acid to a swimming pool that has a copper level could result in a pool filled with green water. This alarming reaction is known as tetrachlorocopper. The green color would be only temporary, but is typically much more alarming to your clientele (the pool owner).

The Technobabble: If we were to add muriatic acid (HCl) to our swimming pool in order to lower the pH and Total Alkalinity, upon addition the acid would disassociate into both Hydrogen (‎H2) and Chloride ions (Cl−). The chloride ions (from the hydrochloric acid) would then displace the H2O molecules in the hexaaquacopper(II) ions [CuH2O)6]2+ causing the water to turn green (four chloride ions replacing six water molecules creating tetrachlorocuprate(II) ions (Cl4Cu). 

Copper(II) hydroxide: Cu(OH)2, photo: Newport Pool Company, Rhode Island

Increasing the pH with caustic soda or soda ash in a pool that has a copper level could result in teal colored staining about the pool. This is known as Copper hydroxide. This is not uncommon in saltwater pools due to by-products from the chlorine production process which also raise the pH.

The Technobabble: If we were to add a dose of caustic soda (sodium hydroxide: NaOH) to the pool to increase pH, the hydroxide ions would then strip the hexaaquacopper(II) ions of hydrogen ions leaving us with the neutral compound copper(II) hydroxide: Cu(OH)2. This complex would precipitate from solution leaving a blue/green (teal) stain. Okay, so we do not typically use caustic soda in pool care nowadays, but we do add other items for chemical balancing that, although they do not contain a hydroxide ion, will create hydroxide ions upon addition (ie: Soda ash (sodium carbonate), phosphates, etc.). For those applications where a saltwater generator (saltwater pool) is used, remember that sodium hydroxide (NaOH) is also produced in the production of chlorine (electrolysis of the saline solution).

Cupric Oxide (CuO); Note: when adding alum as a stain treatment, only use products labeled for pool use, make certain your water chemistry values are in balance, and that you only add enough alum to lightly cover the stain.

If you have a copper level in the water and broadcast your chlorine shock, you could end up with blotchy mottled gray/black stains on the floor of the pool. Extremely startling to a pool tech the first time this occurs, but is usually only a temporary reaction. This is known as Cupric Oxide.

The Technobabble:  If a dose of calcium hypochlorite (CaCl₂O₂) is added to a body of water that contains copper, it is possible that you will see the aftermath of a redox reaction. The chlorine, from the calhypo added, will strip electrons from the copper (oxidize). The result is the insoluble Cupric Oxide (CuO), a black solid, that readily stains. . If caught when freshly converted, this reaction may be reversed in some instances by covering the oxidated area with aluminum sulfate. The charcoal grey color is sometimes converted back to turquoise.

Copper-cyanurate NaCu(C3HN3O3)4.6HO, photo: Perfect Splash LLC, Arizona

A pool with a high stabilizer level and copper in the water can sometimes end up with blotchy reddish-purple staining about the walls and floor. This is called Copper-cyanurate.

Oddly enough there is not a tremendous amount of research on copper-cyanurate (purple crystals), at least not on how it occurs in a swimming pool. What we do know is that when non-chelated Copper is in the presence of a high Cyanuric acid level, the result is the precipitation of tiny purple crystals very similar to Amethyst. Yes!!! The blotchy-purple staining, sometimes referred to as Purple Haze, is actually teeny tiny little four-sided purple crystals. We also are aware that it is quite difficult to rid the pool of the staining (crystals). Chemists, in laboratory applications, have suggested boiling of acids or alkali solutions for mitigation of purple crystals.

I have found these to be relatively soluble using room-temperature acid or a good chelating agent. Boiling-temperature acid is for calcium sulphate… – Que Hales, Pool Chlor

It is important to note that ascorbic acid does not always have the best results when it comes to removing copper stains. The product is better suited to removing those caused by iron. Always test a small area with a Vitamin C tablet before committing to a full pool treatment. Vitamin C is ascorbic acid, so if the tablet is able to remove the stain, the treatment of the pool as a whole should be successful. It is an inexpensive method of testing the product and the reason most Pool Professionals keep a bottle of Vitamin C tablets in their glove box.  Ascorbic acid is an electron donor and can often “bleach” a metal stain by replacing the electron that Chlorine had stripped away.

Ascorbic Acid giveth and Chlorine taketh away…

Note: the folks at onBalance have reported some success in converting turquoise copper stains to white with direct applications of hydrogen peroxide…

The Technobabble: The formula for the compound Coppper-cyanurate, in my opinion, comes into question; Pub Chem lists the structural formula as C3H3Cu3N3O3, ,however the reaction is more likely to mimic other metal cyanurates where a single atom of Copper displaces a single Hydrogen ion. We may find it better represented by Cu(C3N3O3H) as indicated by G. B. Seifer in his research document Cyanuric Acid and Cyanurates. The majority of studies available focus on those minerals created in, and studied in, a laboratory environment by significantly heating the element (Copper) and then dissolving into aqueous ammonia (NH₃) solution. In a 1992 publication titled Characterization of a Crystaline Residue from a Swimming Pool: Disodium Copper(11) Tetrakis (isocyanurate) Hexahydrate (Robert D. Hart, Brian W. Slcelton and Allan H. White – Chemistry Department, University of Western Australia) examining a specimen that had formed in (and was collected from) a swimming pool, the compound was identified as NaCu(C3HN3O3)4.6HO. This was done through X-ray study and chemical analysis.

Crystallized  Poop 

A recent discovery has actually found the compound, or at least something very similar to Copper-cyanurate, to be naturally occurring in what is being credited as a previously unknown mineral. The new mineral, which has been given the name Joanneumite, resembles tiny violet crystals and was found in crevices in rock formations beneath layers of guano (aka: bat excrement). According to the authors (Hans-Peter Bojar, Franz Walter, and Judith Baumgartner) of the research doc, Joanneumite, with a structural formula of Cu(C3N3O3H)(NH3)₂ ,was discovered at Pabellón de Pica Mountain in Chile.

Red, Brown, or Black tinted water = High Iron level

Have we been growing Joanneumite in swimming pools all along? Consider the structural formula Cu(C3N3O3H)(NH3)₂ , then that which the chemists at the University of Western Australia had identified for Copper-cyanurate as NaCu(C3HN3O3)4.6HO. Okay, we get why Copper would be in rocks on a mountain, but where would the Cyanuric acid come from? We know that Cyanuric acid is produced in the heat degradation of urea, so it is feasible that bat guano would contain urea and generate heat as it decays. Over a prolonged period of time, the heat of the decaying bat poop could result in the production of Cyanuric acid (C3N3O3H3). No, we have not been growing Joanneumite; not exactly. The fact that this new mineral has been discovered is significant and my assumptions in its creation takes nothing away from this find. However, the difference between Joanneumite and Copper-cyanurate may simply come down to a pinch of salt (Na), a splash of water (HO) and a dash of ammonia (NH3).

Purple Water = High Manganese level, photo: Legacy Pools, Louisiana

 

Does Copper kill algae?Read More

 

 

Thank you to Que Hales and Kim Skinner, onBalance, for the peer review, contributions, & proof read on this one

Thank you to the Pool Service professionals who had given permission to utilize their photos

References:

Le Moyne College, Transformation of Copper:A Sequence of Chemical Reactions

Pub Chem, Copper;1,3,5-triazinane-2,4,6-trione

Hogg, CHEM2: Chemistry in Your World

Stephanie Pappas, Facts About Copper, Live Science

Cyanuric Acid and Cyanurates, G. B. Seifer, Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii pr. 31, Moscow, 117907 Russia, Received April 17, 2001

GeoScienceWorld.org, Mineralogical Magazine February 01, 2017, Vol.81, Joanneumite, Cu(C3N3O3H2)2(NH3)2, a new mineral from Pabellón de Pica, Chile and the crystal structure of its synthetic analogue

Characterization of a Crystaline Residue from a Swimming Pool: Disodium Copper(11) Tetrakis (isocyanurate) Hexahydrate, Robert D. Hart, Brian W. Slcelton and Allan H. White, Chemistry Department, University of Western Australia

 


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