High Levels of TOC in the Reef

[Cory]

Cory,

I changed the Vortechs for Gyres 1 year ago. Did you hear something about rust in Gyres also?

Rgds,

Daniel

Yes actually there are a few gyre and magnets bursting splitting and rusting. I had one where the cable pulled right out! But id check all sources of metal in your tank. Quite a few people surprised themselves with dying corals only to find out something was rusting. Sometimes it was hinges on a door. Algae scraper magnets. Screws fall in the tank. Sometimes they dont even notice it on an icp! Ive seen metal in sand. Ive seen magnetic black sand! But you must check all your equipment for metal and rust.

 

[Lasse]

Good question. I can repeat the test if necessary.

I tag christoph in my post above because I think he is the person that can answer the question if it is possible to detect elevated concentrations (over the natural level) of fluorine caused by polyfluorinated substances

Sincerely Lasse

 

[Gravity]

Honestly, this seems to just keep spinning around in a circle. So many theories and generally the same suggestion. If this is some strange contaminant (PFAS/Petroleum/Dissolved Carbon...) most of this stuff is typically removed with GAC or Resin. Therefore just get the media reactor full of carbon change it out every few days for a 2-4 weeks and retest TOC, it will drop. Then go back to your normal operation and retest it after a few months to see if it increases again. If this is proven then you have confirmed some source TOC is present in your operation. There is no need to to spend $300 on a PFAS test.

If adding nutrients depletes immediately because of the high TOC then it is biodegradable carbon and would consequently reduce TOC. You just need to take the steps to drop TOC.

Maybe I missed it but are you said you switched water sources to something other refers are using but do you have using RODI? Is the TDS always zero? Do you store your water in an HDPE container?

 

[Lasse]

I think it is very important to stress that OP have - with his own words - succeeded with a lot of other reef tanks during this time - including corals. With the same type of water. Only this system have shown up problems - and the same problems both before and after the change of water sources. It is also for me rather clear that he have tested all standard procedures - with the same result. It is rather clear for me that in this case - the answer is not in the box - it needs to be outside the box.

The reason why I have frozen on the tubes and fittings have different reasons. I have already asked about air cleaners, scented candles smoke and other things in the room and get negative answers The OP have reported success with other systems and location outside any city center but not near the sea - it means that I till now have exclude environmental air quality reasons. What´s left is a source inside the system. My first suggestion was to try to figure out if the high TOC was caused of highly or not easily biodegradable organic carbon. The BOD test - suggested by @Dan_P - is IMO a good tool. IMO better than a test with GAF and ozone because there is organic carbon compounds not easily eliminated by these methods. My main track was and remains this - but I am totally aware that it can end at a railway buffer - but in that case - we know that it was a dead end street.



A last - but a needed question is if this system ever have been treated with remedy's like vibrant or other anti algae drugs?

Sincerely Lasse

 

[josephxsxn]

Have you considered doing one of the tests from here to profile your tank bacteria? https://aquabiomics.com/ IDK why this would be related to your TOC but at this point would be more information. I recall reading some threads where people had corals dying with high levels of vibro bacteria.

 

[Hans-Werner]

One important point is that is very difficult to increase PO4 e NO3 levels in my reef, because the TOC is too high. For example, some reefers uses Vodka as a carbon source to feed bacterias to reduce nutrients level. In my reef - IMO, the same situation happens, but I do not doses Vodka or neither other carbon sources.

This is impossible. (Bacterial) growth is always limited by one or several nutrients. If you would do a constant supply of phosphate and all essential trace elements either all easily degradable TOC like vodka is degraded by bacteria or your tank is filled with bacterial slime after just a few days - exponential growth.

You can remove persistent (to bacterial or other breakdown) TOC compounds with GAC or ozone, and the readily degradable TOC is converted to CO2 and bacterial biomass by bacteria if no other nutrients are lacking.

This means some macro or micronutrients are lacking and this also kills your corals because they need these nutrients too.

I am pretty sure if you don't accept this quite simple conclusion as correct you will not be successfull.

Triton and other ICP-OES laboratories are not the best and most experienced which nutrients are need in which concentrations, because even the application of ICP-OES analysis to reef aquaria is based on some dubious assumptions. ICP-OES analysis is only of limited siginificance for reef aquaria.

Either you have to find out which nutrients are really limiting yourself, or use a good trace elements mix and dose it together with phosphate until you find at least 0.05 ppm phosphate and at least some of the essential trace elements with ICP-OES analysis.

Again, I am quite convinced there is no other way to success.

 

[Lasse]

This is impossible. (Bacterial) growth is always limited by one or several nutrients. If you would do a constant supply of phosphate and all essential trace elements either all easily degradable TOC like vodka is degraded by bacteria or your tank is filled with bacterial slime after just a few days - exponential growth.

You can remove persistent (to bacterial or other breakdown) TOC compounds with GAC or ozone, and the readily degradable TOC is converted to CO2 and bacterial biomass by bacteria if no other nutrients are lacking.

This means some macro or micronutrients are lacking and this also kills your corals because they need these nutrients too.

I am pretty sure if you don't accept this quite simple conclusion as correct you will not be successfull.

Triton and other ICP-OES laboratories are not the best and most experienced which nutrients are need in which concentrations, because even the application of ICP-OES analysis to reef aquaria is based on some dubious assumptions. ICP-OES analysis is only of limited siginificance for reef aquaria.

Either you have to find out which nutrients are really limiting yourself, or use a good trace elements mix and dose it together with phosphate until you find at least 0.05 ppm phosphate and at least some of the essential trace elements with ICP-OES analysis.

Again, I am quite convinced there is no other way to success.

This is wise - but (there is always a but ) in this case I rather sure that there is another problem too and of more chemical nature. But I can be wrong - it has happens before .

I think that the "light" BOD test will give us a partly answer in a day or two.

Sincerely Lasse

 

[paintman]

To eleiminate the PVC pipe question, why not set up a small tank with just a HOB filter. Run your cycle and see if you get the same readings with the small tank. If you do then you know the PVC is the cause.

 

[Randy Holmes-Farley]

To eleiminate the PVC pipe question, why not set up a small tank with just a HOB filter. Run your cycle and see if you get the same readings with the small tank. If you do then you know the PVC is the cause.

How could that rule out everything else that is in the big tank and not in the test tank, including organisms?

 

[Hans-Werner]

there is another problem too and of more chemical nature

This time I don't agree with you, Lasse. At least I am not convinced, yet.

25 years ago it where the green or clear PVC aquarium hoses that killed the corals by chemical softeners/plasticizers. I am convinced today the same hoses won't. We just didn't know what was wrong and something was to blame, something except our lack of knowledge. Today it aren't exactly the PVC hoses, it is something else that has killed our corals, something, except our lack of understanding.

I am pretty convinced, most of our problems are of chemical nature, much more than related to light or current or anything else. But the "chemical problems" are of a different nature than most aquarists think. The "chemical problems" are usually not toxic chemicals of any kind or toxic concentrations of something, but a lack or severe imbalance of nutrients, and a lack of knowledge and understanding from our side, of course.

In the case of phosphate quite exactly the opposite seems to be true than what has been told over the last decades. There is no detrimental excess in phosphate but only starving low concentrations.

Recently I saw a nano tank and the corals looked quite normal and even pretty colorfull. The corals were not thin or of other bad or abnormal growth at all. The phosphate concentration was between 2 and 3 ppm, no "0" lacking. With the the ULR test and photometer it was "out of range", with our "Pro" test it was obviously darker than the darkest blue, finally with our "Basic" test I was able to get a result.

With nitrate it is similar, just vice versa, there is no necessity, only detrimental effects.

 

[Lasse]

Yes I totally agree with you about nutrient levels - but it is not PVC tubes with softeners I´m worried about. He had use these pipe details that is used for indoor waste water

The part inside the red ring contains a fitting and when you mount these you need some fat.

1) For some years ago it was common with anti mold treatment of these type of pipes - but in this case - the producer had answer the OP that they are not treated at all against mold. This is sorted out as not valid at the moment

2) The next question is if they are treated with a flame retardant or not.There is a lot of Polyfluorinated substances (they are organic) that is used as flame retardants. This is not sorted out yet

3) The fittings this type have rubber/plastic fittings. There is fittings that contain nitrile as acrylonitrile rubber - this type of rubber should not be toxic according to some sources. The same about SBR (Styrene-Butadiene rubber) but in that case there is conflicting reports according to soccer field of artificial grass. This is not sorted out completely yet.

4) The lubricant that was in use when they mounted the system 6 years ago, This type of fittings must be lubricated before you put the pipes together Because I have use this type of pipes in small and temporary installations - I always use butter as lubricant. But the normal is other types. There is a lot - I did a small search on the types that is available in Sweden and found at least on with serve ecoltoxilogic effects in water. Not sorted out yet

I´m not sure that I´m on right track but - IMO - this three objections that are not sorted out yet need to be sorted out.

Of cause - there is nothing that talks against using higher nutrient levels and trace elements already now - before my objections is ruled out (or confirmed) - but the best with me (and sometime the worst of me according to my wife) is if you compare me and a donkey - its the donkey that is the diplomate

Sincerely Lasse

 

[Hans-Werner]

Yes, Lasse, I know. I must say, I use the same pipes from the construction market. They are incredilby flexible and available in a lot of angles. The water hardly gets in touch with the seal rings, I think, not much flow at the seal rings.

I wash the lubricant off of the seal rings and use water or spit.

Usually I absolutely agree with you, in nearly all of your contributions, but this time not.

 

[Lasse]

Usually I absolutely agree with you, in nearly all of your contributions, but this time not.

It always need to be a first time

Maybe I can say the same.........

I have used outdoor waste water pipes (the orange/red ones) in many constructions of fish farms but before we used them we carefully examined how they were made and what type of seals were used. We also used butter as a lubricant. When we did these surveys, it was clear that there were types that were not so suitable to use. I do not know which types that is normal in Brasil but according to the long time and the OP only have had problems with this system - I still think it is important to totally rule it out or confirm.

Sincerely Lasse

 

[Daniel Almeida Prado]

Yes actually there are a few gyre and magnets bursting splitting and rusting. I had one where the cable pulled right out! But id check all sources of metal in your tank. Quite a few people surprised themselves with dying corals only to find out something was rusting. Sometimes it was hinges on a door. Algae scraper magnets. Screws fall in the tank. Sometimes they dont even notice it on an icp! Ive seen metal in sand. Ive seen magnetic black sand! But you must check all your equipment for metal and rust.

Hello Cory,

Many thanks for the advice. I will check that magnets and the eventually rust.

Rgds,

Daniel

 

[Daniel Almeida Prado]

I tag christoph in my post above because I think he is the person that can answer the question if it is possible to detect elevated concentrations (over the natural level) of fluorine caused by polyfluorinated substances

Sincerely Lasse

Perfect Lasse,

I am waiting Christoph answer.

Rgds,

Daniel

 

[Daniel Almeida Prado]

Honestly, this seems to just keep spinning around in a circle. So many theories and generally the same suggestion. If this is some strange contaminant (PFAS/Petroleum/Dissolved Carbon...) most of this stuff is typically removed with GAC or Resin. Therefore just get the media reactor full of carbon change it out every few days for a 2-4 weeks and retest TOC, it will drop. Then go back to your normal operation and retest it after a few months to see if it increases again. If this is proven then you have confirmed some source TOC is present in your operation. There is no need to to spend $300 on a PFAS test.

If adding nutrients depletes immediately because of the high TOC then it is biodegradable carbon and would consequently reduce TOC. You just need to take the steps to drop TOC.

Maybe I missed it but are you said you switched water sources to something other refers are using but do you have using RODI? Is the TDS always zero? Do you store your water in an HDPE container?

Hello Gravity,

Excelent idea about GAC filter, but once that I restart the reef a lot of times and the TOC is always high, I think that the TOC source still in activity. Do you agree? However, that idea is IMO a very good idea. The RO/DI is always test by TDS and ICP. A lot of friends use the same water in their reefs with success!!!!

Rgds,

Daniel

 

[Daniel Almeida Prado]

I think it is very important to stress that OP have - with his own words - succeeded with a lot of other reef tanks during this time - including corals. With the same type of water. Only this system have shown up problems - and the same problems both before and after the change of water sources. It is also for me rather clear that he have tested all standard procedures - with the same result. It is rather clear for me that in this case - the answer is not in the box - it needs to be outside the box.

The reason why I have frozen on the tubes and fittings have different reasons. I have already asked about air cleaners, scented candles smoke and other things in the room and get negative answers The OP have reported success with other systems and location outside any city center but not near the sea - it means that I till now have exclude environmental air quality reasons. What´s left is a source inside the system. My first suggestion was to try to figure out if the high TOC was caused of highly or not easily biodegradable organic carbon. The BOD test - suggested by @Dan_P - is IMO a good tool. IMO better than a test with GAF and ozone because there is organic carbon compounds not easily eliminated by these methods. My main track was and remains this - but I am totally aware that it can end at a railway buffer - but in that case - we know that it was a dead end street.



A last - but a needed question is if this system ever have been treated with remedy's like vibrant or other anti algae drugs?

Sincerely Lasse

That’s exactly what’s happening here. The problem is outside the box Lasse!!!

I used to do the BOD5, a Sera test for Dissolved O2. At the beginning of the test the result was 4mg/l and the result after 5 days was the same. However, I will be honest I do not know if that Sera test is really accurate. I have my doubts about. I am trying to check in the Sera website if this test can be use for sweet and marine water, because I do not found in the box any mention about the marine use of the test. Is there anybody know about?

One time I used fluconazole do kill bryopsis, only this.

Rgds,

Daniel

 

[Daniel Almeida Prado]

This is impossible. (Bacterial) growth is always limited by one or several nutrients. If you would do a constant supply of phosphate and all essential trace elements either all easily degradable TOC like vodka is degraded by bacteria or your tank is filled with bacterial slime after just a few days - exponential growth.

You can remove persistent (to bacterial or other breakdown) TOC compounds with GAC or ozone, and the readily degradable TOC is converted to CO2 and bacterial biomass by bacteria if no other nutrients are lacking.

This means some macro or micronutrients are lacking and this also kills your corals because they need these nutrients too.

I am pretty sure if you don't accept this quite simple conclusion as correct you will not be successfull.

Triton and other ICP-OES laboratories are not the best and most experienced which nutrients are need in which concentrations, because even the application of ICP-OES analysis to reef aquaria is based on some dubious assumptions. ICP-OES analysis is only of limited siginificance for reef aquaria.

Either you have to find out which nutrients are really limiting yourself, or use a good trace elements mix and dose it together with phosphate until you find at least 0.05 ppm phosphate and at least some of the essential trace elements with ICP-OES analysis.

Again, I am quite convinced there is no other way to success.

Hello Hans,

As I told you I already use a lot of phosphate daily in the tank with no improvement. However, I can do this again. Do you recommend what kind of product to increase phosphate level? Because as I told you it is very very difficult to increase the phosphate level in the tank.

You told about that is possible to remove the TOC with ozone. How can you would do that? Because I used ozone until 350ppm ORP, with no better results in TOC. To use more levels of Ozone can be dangerous for fishes.

Rgds,

Daniel

 

[Hans-Werner]

Hello Lasse,
Even if there is something toxic released by the pipework and even if the plasticizers of 25 year ago released where toxic, which I don't think, there is no way for us to find out except to create otherwise perfect conditions. Since we are not all that good in creating perfect conditions for corals yet, it is very difficult in my eyes to blame any toxin for failures. So I only want to say, we have to do the first step first and create otherwise perfect conditions. Otherwise we will fail anyway, no matter if there is something toxic in the water.

Even improvements can lead to failure when the other conditions are not perfect, because any imbalance in nutrients gets more severe with improvements in other fields. For example I think LED is a hughe improvement, as soon as we learn to handle nutrients better.

Hello Daniel,
I hardly ever applied ozone. I know it is used to remove yellow substances (maybe fulvic acids?) and I think aggressive chemicals that are able to remove these persistent yellow substances are able to crack and degrade most organic substances, and bacteria will do the rest. I think the normal application of ozone is to supply it to the skimmer.

Similar with GAC, just the very normal application should help with most organic substances.

Also water changes for sure are suitable to remove toxins, my guarantee. If the tank is not extremely big I recommend a trial with 25 to 50 % water change. A 50 % water change usually is no problem at all for corals, I have tried it frequently. In this way you can make any toxin unlikely. Any TOC can be removed with water changes.

To raise the phosphate concentration nearly every soluble phosphate salt should work, orthophosphates of sodium or potassium, pyro or polyphosphates of sodium and even phosphates of calcium should be sufficiently soluble.

Some forms of phosphate may be more appropriate than others. The problem with phosphate is, that a lot of phosphate is adsorbed to exhausted rocks, sand and any calcareous material in the tank before you get free phosphate in the water. So you maybe will have to dose a lot of phosphate slowly, control the concentration regularly and at first you will hardly find any success, and suddenly phosphate concentration jumps up. This is not easy to handle.

A balanced trace elements supply is just as important because Liebig's law of the minimum applies also to micronutrients, the nutrient in shortest supply will limit success.

Regards

Hans-Werner

 

[Lasse]

Easy to check if the test is good or not. Take a sample of water - do the test - add some organic waste and some ml of vodka to the sample (maybe some fish food too) Let is stand for 5 to 10 days - measure the O2. If the O2 not is near zero when you do the retest - the test will not work,

I have a question that I have forget to ask. You say that your corals dies. How do they die? fast or slow? during a day or during a week or even months?

Yes it take times to rise the PO4 if all reserves was exhausted of the reasons that Hans-Werner mentioned and I have to admit that the fact that it takes time for you to rise the PO4 may indicate a very limited PO4 pool. But if you add PO4 with a dosing pump - do it when the light is on.

Hans-Werner - in any other case with low growth and death of corals I have seen here at R2R - I would be 110 % on your side about nutrient defiency. However this seems to be different when I read through the thread. However - if the fish have died too - my case have been stronger

I have seen maybe 100 N-DOC tests and no one have had a value of over 8.5 ppm TOC in spite of how nutrient rich the aquarium have been and in spite of the use of DOC (alcohol). Among aquarium tested is my own (rather nutrient rich) and a system where PO4 is around 0.4, NO3 around 100 and temp around 12 degree C (low bacterial consumption of organic carbon). In OP:s tank TOC was above 12 ppm

The OP seems to be a rather experienced saltwater aquarist with success with a lot of other systems.

I still believe that the nature of the TOC in this case is the main key - fast followed by your suggestions.

@Daniel Almeida Prado Wastewater treatments plants use to do BOD5 (or BOD7) - Are there any near your location? Or a university or highschool with good equipments?

Sincerely Lasse