Lanthanum Chloride vs Cerium Chloride (My Fish Are Dying)

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Ben Pedersen

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I'd think your tank could easily operate above .1 ppm of phosphate but growth will be slower. The corals look great. I'm truly sorry for your loss. Like others have said, do some water changes and use a LC product until you slowly get the level to stay down. That'll take quite a while. In the meantime, put in more clean-up crewmembers to help with the turf algae. If you have elevated nitrate also, a cheato fuge and some iron can help.
Have a refugium full of algae and clams. Ya.. very sad.. hope the rest of the fish last the night.
 
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Ben Pedersen

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After all the water changes, I added 2 reactors full of carbon and zeolite. Whatever caused the issue with the fish is probably not in the tank any longer but they are all still breathing heavily. Really can't do any more.
 
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Ben Pedersen

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How about adding an airstone to increase oxygenation?
Not sure if an air stone would increase the O2 saturated more then my protein skimmer. I have also heard that to many fine bubbles in water can irritate fish gills. Thanks for the suggestion though.
 

Randy Holmes-Farley

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Not sure if an air stone would increase the O2 saturated more then my protein skimmer. I have also heard that to many fine bubbles in water can irritate fish gills. Thanks for the suggestion though.

i wouldn't assume that a skimmer allows the tank to attain O2 saturation at night, but it certainly helps.
 
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Ben Pedersen

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As of this morning, the female bird wrasse is dead, the lemon-peal angle is missing, and a cleaner wrasse is missing. No negative impact on the coral, snails, anemones, or clams.

The remaining fish are acting pretty normal, eating, but still breathing heavier then usual.

Hope I don't end up with fish with permanent emphysema.
 

Dkeller_nc

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Very sorry to hear about your loss. Those of us that have been in the hobby for any length of time have felt the pain of losing a fish that's new, whether in QT or the display tank. But in my opinion it's much worse to lose fish that we've had for years.

On the subject of cerium vs. lanthanum chloride, one of the aspects of using lanthanum chloride is that it nearly instantly transforms from the soluble chloride form to the nearly completely insoluble phosphate form. As I mentioned in another post, this conversion has an analogy with Barium - barium is incredibly toxic (to humans) in its soluble barium chloride form. However, because of the nearly complete insolubility of barium sulfate, doctors regularly use what would otherwise be an absolutely fatal dose of barium in the barium sulfate form as a radiological tracer with no ill effects on the patient.

In that post, I speculated that lanthanum might be OK because any "leftover" lanthanum that doesn't get instantly converted to the insoluble lanthanum phosphate would be converted to (what I speculated) would be an insoluble lanthanum sulfate form. Stupid me, I didn't look up the solubility constant of lanthanum sulfate before I made that post. It appears that lanthanum sulfate is actually moderately soluble in water.

This might, or might not, explain fish toxicity reactions from users of lanthanum chloride for phosphate removal. Like Randy, I have questions about the validity of the explanation that insoluble lanthanum phosphate particles is the cause of the toxicity. The post above noting that several rare earths produce toxicity reactions in fish (with cerium being the most toxic to marine fish, and lanthanum being the most toxic to freshwater fish) suggests a possible explanation as to why some folks use lanthanum chloride for phosphate removal with no issues, and others lose fish from doing so.

In tank water with a good deal of inorganic phosphate, if one doses just a little of a lanthanum chloride solution, then absolutely all of it will very, very quickly get converted to completely insoluble lanthanum phosphate and be removed by mechanical filtration, or simply precipitate out on surfaces and not cause any harm. The question about lanthanum use is what happens when more lanthanum is used than can be precipitated out as lanthanum phosphate. If there's other anions in typical marine water that form nearly insoluble compounds with lanthanum, then "excess lanthanum" wouldn't be of concern - any lanthanum over and above what would be stoichiometrically taken up by phosphate will be precipitated by the other anions and (probably) not cause harm.

However, and this would apply equally to cerium that forms compounds with similar solubilities as lanthanum (or insoluble, as is the case with lanthanum and/or cerium phosphate), if there's not a counter-ion in typical tank water that's available to "take up" any excess lanthanum or cerium as lanthanum/cerium phosphate, then one would expect significant lanthanum/cerium to remain in soluble form in the tank water, and would be available to potentially cause toxic fish reactions.

Really verifying the above speculation will require looking through an extensive list of the major, minor and trace anions in seawater, looking up the solubility of that ionic compound with lanthanum and/or cerium, and determining that if the particular lanthanum/cerium ionic compound is nearly completely insoluble, whether there's enough of that anion in typical tank water to completely consume any remaining lanthanum/cerium that's leftover from forming lanthanum/cerium phosphate.
 
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Ben Pedersen

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Very sorry to hear about your loss. Those of us that have been in the hobby for any length of time have felt the pain of losing a fish that's new, whether in QT or the display tank. But in my opinion it's much worse to lose fish that we've had for years.

On the subject of cerium vs. lanthanum chloride, one of the aspects of using lanthanum chloride is that it nearly instantly transforms from the soluble chloride form to the nearly completely insoluble phosphate form. As I mentioned in another post, this conversion has an analogy with Barium - barium is incredibly toxic (to humans) in its soluble barium chloride form. However, because of the nearly complete insolubility of barium sulfate, doctors regularly use what would otherwise be an absolutely fatal dose of barium in the barium sulfate form as a radiological tracer with no ill effects on the patient.

In that post, I speculated that lanthanum might be OK because any "leftover" lanthanum that doesn't get instantly converted to the insoluble lanthanum phosphate would be converted to (what I speculated) would be an insoluble lanthanum sulfate form. Stupid me, I didn't look up the solubility constant of lanthanum sulfate before I made that post. It appears that lanthanum sulfate is actually moderately soluble in water.

This might, or might not, explain fish toxicity reactions from users of lanthanum chloride for phosphate removal. Like Randy, I have questions about the validity of the explanation that insoluble lanthanum phosphate particles is the cause of the toxicity. The post above noting that several rare earths produce toxicity reactions in fish (with cerium being the most toxic to marine fish, and lanthanum being the most toxic to freshwater fish) suggests a possible explanation as to why some folks use lanthanum chloride for phosphate removal with no issues, and others lose fish from doing so.

In tank water with a good deal of inorganic phosphate, if one doses just a little of a lanthanum chloride solution, then absolutely all of it will very, very quickly get converted to completely insoluble lanthanum phosphate and be removed by mechanical filtration, or simply precipitate out on surfaces and not cause any harm. The question about lanthanum use is what happens when more lanthanum is used than can be precipitated out as lanthanum phosphate. If there's other anions in typical marine water that form nearly insoluble compounds with lanthanum, then "excess lanthanum" wouldn't be of concern - any lanthanum over and above what would be stoichiometrically taken up by phosphate will be precipitated by the other anions and (probably) not cause harm.

However, and this would apply equally to cerium that forms compounds with similar solubilities as lanthanum (or insoluble, as is the case with lanthanum and/or cerium phosphate), if there's not a counter-ion in typical tank water that's available to "take up" any excess lanthanum or cerium as lanthanum/cerium phosphate, then one would expect significant lanthanum/cerium to remain in soluble form in the tank water, and would be available to potentially cause toxic fish reactions.

Really verifying the above speculation will require looking through an extensive list of the major, minor and trace anions in seawater, looking up the solubility of that ionic compound with lanthanum and/or cerium, and determining that if the particular lanthanum/cerium ionic compound is nearly completely insoluble, whether there's enough of that anion in typical tank water to completely consume any remaining lanthanum/cerium that's leftover from forming lanthanum/cerium phosphate.
I completely agree.. So much is un known and not really testable regarding full and patial reactions and by products. In this case the manufacture changed the formula of the product from lanthanum chloride to cerium chloride because cerium bonds to phosphate quicker then lanthanum. Aperently the toxicity for cerium is much higher for marine fish as compared to fresh water fish.

In regards to my situation, I added .03 mL to my skimmer... I had high phosphates.... so I think that all or almost all of the cerium was rendered inert. However, the manufacture said that there were other harmless salts as a byproduct of the manufacturing process in the product as well. There is no way to really know what killed the fish.. This product is obviously not safe for marine use. I just wish the manufacture had updated the spec sheet identifying that it was Cerium based. :(

Ya.. this is the biggest fish loss I have ever had.. Been reefing for 38/39 years... that tank is 10+ years old.. the chromis have been there for over 8 years.. and the other fish for many years..

A strange coincidence... All the fish that died were the most aggressive fish (bosses) Powder Brown Tang, Female Bird Wrasse, Lemon Peal Angle.. except for the Foxface.

Very sad.. almost made me cry to see the male bird wrasse lay down next to the female.. Now he is swimming around recognizing that the female is missing.
 
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LouCiro

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Last night after much consideration and reading I dosed 0.4 mL of Orenda PR-10,000 directly into my skimmer to reduce phosphates. This morning thinking I would add the manual dosing to my morning routine, I added another 0.3 mL. After doing this I noticed that my fish were all breathing very hard and that my Powder Brown tang was missing. The tang was dead and my fox face died shortly after.

The tank is approx 90 gallons. The water is not and was never cloudy. I have done a 15 gallon water change and am making water to do another 15 gallon change. All fish are still breathing heavily.

I called the manufacture who said they had switched from Lanthanum Chloride to Cerium Chloride 15 years ago. They also said they had no idea what would have killed the fish especially at the small dose I used. Cerium Chloride produces a similar inert flux as Lanthanum Chloride.

Does anyone have any idea why this would be killing my fish.. I am really concerned I am going to loose my Wrasses and Tangs. All corals and invertebrates look great.

Any info would be helpful. :(
Do a complete water change. Had similar issues with a 3000 gal tank. Stuff becomes toxic after it precipitates phosphate. Fish recover immediately in new water.
 

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One thing to try if possible is to move a fish or two into a bucket of fresh SW. If the fish seems better, maybe the chemical is still in the tank. I had used a chemical to kill blue clove polyps years back. The chemical got into the rocks and leached back out for months. I did massive water changes but it didn't help. I had to ride it out using carbon and replacing it weekly until the chemical was gone.
 
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Ben Pedersen

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Do a complete water change. Had similar issues with a 3000 gal tank. Stuff becomes toxic after it precipitates phosphate. Fish recover immediately in new water.
Lost 4 fish.. All others seem to be recovering.. All are eating and acting normal but still breathing a little faster then normal.

Did a big water change and added 2 carbon and zeolite reactors.
 
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Ben Pedersen

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One thing to try if possible is to move a fish or two into a bucket of fresh SW. If the fish seems better, maybe the chemical is still in the tank. I had used a chemical to kill blue clove polyps years back. The chemical got into the rocks and leached back out for months. I did massive water changes but it didn't help. I had to ride it out using carbon and replacing it weekly until the chemical was gone.
I did put one of the fish in a pond down stairs.. It still died.

Added 2 reactors with carbon and zeolite.. Remaining fish seem to be recovering.
 
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I assume it is a different form of Cerium chloride as the data sheet for the product does not list any of the same hazards. The product datasheet also says that it is safe for fish and invertebrates.

Cerium trichloride heptahydrate looks pretty nasty. :(
The element, Cerium, has 2 stable oxidation states, +3, and +4. So you will either have Cerium trichloride, or Cerium tetrachloride, which is also toxic. Here is the MSDS for CeCl4 https://fscimage.fishersci.com/msds/04387.htm

Heptahydrate just means there are 5 water molecules for every CeCl4 in the crystal matrix. When it dissolves it just becomes part of your aquarium water and has no effect on the properties of the compound in solution.

Also, there is only 1 stable isotope of Cerium, which has an 88% natural abundance, so it's definitely possible there could be some radioactivity going on as well. Although judging by the extremely long halflife of the most common radioactivity isotope, it probably isn't super radioactive.

I would just stay away from heavy metals in general.
 

Randy Holmes-Farley

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The element, Cerium, has 2 stable oxidation states, +3, and +4. So you will either have Cerium trichloride, or Cerium tetrachloride, which is also toxic. Here is the MSDS for CeCl4 https://fscimage.fishersci.com/msds/04387.htm

Heptahydrate just means there are 5 water molecules for every CeCl4 in the crystal matrix. When it dissolves it just becomes part of your aquarium water and has no effect on the properties of the compound in solution.

Also, there is only 1 stable isotope of Cerium, which has an 88% natural abundance, so it's definitely possible there could be some radioactivity going on as well. Although judging by the extremely long halflife of the most common radioactivity isotope, it probably isn't super radioactive.

I would just stay away from heavy metals in general.

These suggestions are just not reasonable, IMO
.

There's no chance the material is cerium tetrachloride, and no chance it is a radioactive isotope that caused the issue.

I suggest we not muddy the waters discussing the toxicity of things it is not.

The product here is a cheap bulk chemical to treat swimming pools, and in a quick search, I was unable to find any company that sells cerium tetrachloride, even specialty chemical companies that have many different variations of cerium trichloride. As to radioisotopes,, that is just beyond the pale in terms of suggesting it is the issue here. Radioisotopes are very, very expensive.
 
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Ben Pedersen

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Almost certainly it was Cerium tri-chloride.. After discussing with the manufacture, they said there were traces of lead, copper and other metals but near undetectable (99.999 pure).

Pretty sure the negative affect on the fish was do to the Cerium toxcicity not metal nor radioactive properties..

The end result was 4 fish lost (Powder Brown, Bird Wrasse, Foxface & Lemon-Peal Angle).. 12 fish survived and no other organisms visually impacted. All fish are eating and breathing normally. It took 3 days to get back to normal... all from a total of 0.6mL of Cerium Chloride being injected into my skimmer (2 doses of 0.3mL).

All of this my fault for not verifying with the vender and sighting old posts where this product was used. Clearly Cerium Chloride is not safe for marine fish.. and when purchasing a phosphate reducer, verify that it is 100% Lanthanum based. Manufactures change ingredeience without updating chemical spec sheets and listed ingedience.. Probably more manufactures have and will switch to Cerium due to it's greater affinity to Phosphates.
 
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