Monday, July 05, 2010

Lanthanum Phosphate

As you know, I've built this nice new pool. The pool is designed to stay at 85 F for most of the year, and so it has solar panels in their own insulated glass boxes so that it can collect heat even when the outside air temperature is low. Because those panels can get ridiculously hot (338 F) in the sun when water is not flowing through them, they are made of copper rather than plastic as is more commonly done. I've been learning the consequences of that difference.

A couple weeks after filling the pool I added chlorine (hypochlorous acid, HClO), which immediately caused a brown stain on my nice white plaster pool. Copper from the panels had leached into the pool water in the form of copper ions. The HClO oxidized those ions, probably to Cu2O, which promptly came out of solution and bound to the plaster. So, now I have a brown pool. It really pissed me off for a while, but I've grown used to the look and now I actually think it looks good in some places. One of the interesting side effects of having all this copper in the water is that the copper is antimicrobial. The pool has often gone for days with zero chlorine, at 92 F, and with tons of phosphate, and has essentially no algae growth. Without copper that would be a recipe for an algae bloom.

I have these little strips that claim to test the copper content of the water, and that test result drops to zero shortly after I add chlorine. After four or five days it will bounce back up to 0.5 ppm (ppm meaning mg/liter in this case). That means my 38500 gallon pool has 2.5 ounces of copper in it that used to be on the roof. Clearly I can't go on like this for too long, or I'm going to have pinhole leaks in the roof panels. Happily, I've noticed recently that the copper seems to be zero even after a few days of no chlorine, and if this is real, it means the copper has stopped leaching into the water, perhaps because I now have a protective patina on the interior of the pipes.

In my various attempts to keep my white plaster white, I added "chelating agents" to the pool. These things are basically dish soap, and load the water with lots of phosphate (HPO4 2-). The idea is that the phosphate ion will preferentially bind to the copper ions and form Cu3(PO4)2, which is insoluble in water. Presumably this copper phosphate doesn't bind to the plaster but instead can be filtered out. In combination with a low pH this was supposed to reduce the Cu2O in the plaster, then convert it to Cu3(PO4)2, but if that was happening it sure wasn't obvious. I eventually gave up. This exercise left the pool with over 2500 ppb phosphate, which is way too high. When the copper levels recently stopped going up without chlorine, an interesting thing happened: algae! So this weekend I determined that it was time to take out that phosphate.

One takes out phosphate by adding Lanthanum Chloride. This reacts with the phosphate to make LaPO4, which immediately comes out of solution and forms this white fluffy stuff on the bottom of the pool. I tried vacuuming this up -- big mistake. The stuff will plug any filter, instantly. I tried a few times adding lots of DE to the filter, and gave up. That's when I read online that you have to vacuum this stuff out of your pool entirely, just dumping the water to the street. Then I realized I hadn't really plumbed my pool with an option to vacuum to waste. D'oh!

[Update: fixed the plumbing so I can now pump to the street or sewer. Since I have very low-resistance pipes, it looks like I can pump over 80 gallons/minute to the street, which is very impressive to see.]

For a little while I was feeling pretty beaten. The phosphate levels weren't reading any lower, the pool was a mess, I had no plan to get it clean, and my fingernails were gone from cleaning the DE out of the backwash tank. This Lanthanum Phosphate is amazing -- a tiny amount turns DE into a watertight membrane, something like Bentonite clay.

Then I got back to work. I pumped the water out of the spa, then set the valves to bypass both the filter and backwash tank, suck from the pool and return to the spa. With my vacuum in place I was vacuuming the pool into the spa. Before turning on the pump I put a sump pump in the spa and pumped it out into a hose which went to the sewer. Yes, this was pumping phosphates into the city's sewer. I think I pumped out about 2.5 pounds of phosphate, or about one box of dishwashing detergent. I had no copper in the water, nor any chlorine, and my pH was 7.5. It shouldn't be a problem for anything downstream. The vacuum sucked everything off the bottom and we dumped about 800 gallons of water, or $2.40. Even better, my phosphate is now down to 300 ppb, which isn't perfect but it's nice to be out of the unmeasurable range.

In doing the research for this blog post I found out that my tap water already has around 190 ppb phosphate in it, added by Los Altos to control corrosion in copper pipes. So, I need to measure my copper levels now that I have low phosphate to see if I'm back into corroding my solar panels. Hopefully something else is protecting the panels.

Also, I've learned that the patina that can protect copper is soluble in ammonium salts. That's significant because ammonia in the pool is what you measure when you measure "combined chlorine" (really chloramines). It seems I'm going to have to stay on top of that, not just because chloramines are smelly eye irritants, but because the stuff attacks my panels.

I can keep after it with adding chlorine, but my main line of defense was supposed to be a nightly dose of ozone, intended to burn anything organic down to N2, CO2, and water. The ozone is on hold until I can re-cover my DE filter grids in stainless steel mesh, instead of the polypropylene mesh they have now. Meh. More work. Some other weekend.

[Update: stainless steel mesh won't hold diatomaceous earth. I got some mesh samples and tried pouring DE mud on them, and it fell right through. Under the microscope, it's clear that DE grains are just tens of microns across, and so a macroscoping mesh isn't going to do it.

I've read that glass is compatible with ozone, so I'm going to try fiberglass as a filter material to hold the DE, and we'll see how that goes.]

[Update2: BGF fiberglass filter fabric style 421 style 580 holds diatomaceous earth just fine. I had to hand sew it with stainless steel wire, since fiberglass strands are completely useless for sewing, as they fray and break at the slightest provocation. Next up: long term test of fiberglass grid covering to see if it breaks or does some other bad thing.]


  1. I had a pool in Dallas for close to 30 years. My neighbors used to curse pool maintenance but if they'd have stayed awake during high school chemistry it would have been like baking brownies.

    The best way to deal with algae is to add lanthanum carbonate to selectively bind trhe phosphorous in the pool's water. No available phosphorous; no algae. Determine or estimate the amount of phosphorous and add lanthanum accodingly. Lanthanum carbonate has become hard to find at retail since the FDA screwed up the equation by allowing it to be sold as a prescrioptiuon drug, Fosreno to bind excessive phosphorous in vitro.

    There are devices sold, I believe by Leslie's, that I've used to remoive copper stains. They allow you to flow phosphoric acid into a very localized area/volume that you guide over the stains.

    Eliminate chloramines: A small amount will arsise from sweat but stop urinating in the pooland the level will go down fast.

  2. PhosFree sold at Leslie's Pools removes the phosphates. Beautec, sequesters the metals (and adds no phosphates) it also sequesters the calcium. Great stuff! and DE is nasty horrible stuff, its a class1 carcinogen! Try "FIBER CLEAR" instead. Its bio-degradable clean & green. website: HOWEVER!!!! While fiber clear is AWESOME! it will only work with a maintenance dose of PhosFree not a full scale removal. DE filters down to 4 micrograms Fiber Clear filters down to 2 micrograms, some filters get way to efficient with both products.

  3. I have used PhosFree, which I think is just Lanthanum Chloride. Beautec sounds nice, but I think I don't like the copper dissolving from the panels in the first place. I'm going to install a titanium heat exchanger between the panels and the pool, and kill the problem dead.

  4. I work at a pool store and I'm attending the University of Notre Dame with a major in Mechanical Engineering and a minor in Bioengineering. And I must say I very much enjoyed reading this. I wish I could have a customer like you haha. I love to understand the chemistry of what I sell, but I rarely have anyone at the store who feels the same way :(

  5. I would put borate technology up against phosphate removers any day of the week.

  6. Andrew S. Mooney2:01 PM, April 06, 2012

    Have you tried getting one of these? : A Floatron means you don't need Chlorine and avoids trashing your water pipes as it produces the Copper ions in your water via electricity.

    and a description of the chemistry here:

  7. A Floatron or any other system that injected copper ions into the pool directly might keep the panels from dissolving quite so fast, but it's still going to suffer the problem of oxidized copper staining the plaster. No thanks.

  8. Current published pool maintenance theory is nonsense. It requires addition of hardness supposedly to prevent dissolution of pool walls. This theory is based on chem eng papers published in the 30's for concrete sewer pipes. If you add hardness you will constantly be adding acid to bring the pH down to 7.2 the pH ofant naco3 solution will always go to 8.3 ,,,,the best way to maintain a pool is to start with deionized or RO water and add nothing but NaCl for a chlorine generator. Chlorine can be held at 1ppm with no problem
    Pool grade or USP grade salt is needed to prevent addition of iron or other unwanted ions. LaCl3 is the correct chemical to use for
    Phosphate removal . We use it in our salt water fish tanks for this purpose. It will starve out the algae. I have maintained a pool for 20 plus years with no problems using these methods with a Hayward 4000 cartridge filter. Look up the old " balanced pool " nonsense references.