High Levels of TOC in the Reef

Daniel Almeida Prado · Jan 7, 2021

Cory said:
Wouldn't those numbers be basically nearly zero? Can you experiment in a separate tank and dose no3 and po4 with a coral?

Hello Cory,

I agree with you, but I have had other reefs and IMO, when corals die by poor nutrients, the kind of the death is very, very different. I mean, in a reef tank with ultra lown nutrients, the death of corals happens very slown, different from my tank. Thea death of hard corals in my tank in some occasions occurs just in a few days.

Rgds,

Daniel

Daniel Almeida Prado · Jan 7, 2021

Hans-Werner said:
I am sorry that I did not read the complete threat, but at page 2 I saw what your problem is. TOC is maybe an indicator for bad overall conditions, that might be correct.
The reason for your problems is an extremely low phosphate concentration (12 µg/l = 12 ppb = 0.01 ppm). This is the reason why nitrate and TOC builds up and it is also the reason why all your corals die. Corals absolutely don't tolerate such wide N : P ratios (marked red by Triton) and low phosphate concentrations at the same time, see also here.

Hello Hans-Werner,

Many thanks for your answer.

I understand your point of view. As I said to Cory, I have had a lot of other reefs in the last years and the kind of the death of my corals in my reef is very different from the death of starveling corals.

A few months ago I increase the level of PO4 to 0.08-0.1. The corals continued to die by the same way, unfortunately!!!

Rgds,

Daniel

Daniel Almeida Prado · Jan 7, 2021

Lasse said:
@Daniel Almeida Prado You aquarium have been in function for over 6 years and you have reported the same problems for all these years - not only for hard corals but even for softies of different species. The very low PO4 and NO3 is a problem in every aquarium (IMO) in spite of other evenual problems. The question is now - have you have these low readings for all 6 years? If it turn out with a high BOD5 - @Hans-Werner :s suggestion maybe is the way to go.

IMO - it is important that you also try to validate your nitrate level - you report 0.1 ppm nitrate with your test - Triton report over 4 ppm in TN - corresponding to over 18 ppm NO3 if all was in that form. You report 0.1 in measured NO3 - this make no sense - Either is your own NO3 measurements totally wrong or the detected TN level by Triton refers to another source of N than NO3.

IMO - it is more and more important to track the source of the high organic C - because the result will decide which main path to follow. I agree with Hans-Werner (and others) that have point out the low PO4 concentrations - it needs to be raised. But - because of the long history of your problems - I´m not sure if it is the main problem for you.

Beside a possible treatment of the pipes (with anti mold agents) - you may have to look at the rubber gaskets too.

If they are nitrile treated - both the high TOC and the high TN can be explained - here is the general formula for nitrile:
R-N≡C. R is an optional organic compound

Sincerely Lasse

Hello Lasse,

I answered the question about low PO4 for Cory and Hans. In sum, even with higher PO4 levels, the corals continued to die by the same way. Nothing change when I increased.

Lets me explained a little bit more things for you guys. In the last 6 years, I rebuild the reef at least 6 times.

I tryed everything that you can think. One time, I rebuild the reef changing all of the live rocks, in other rebuild I change the substrate, I also triyed to change all of the pipes, I changed the thermostates, the pumps, the skimmers.

Believe me my friends, I changed the glass of the aquarium

I tryed a lot of methods as Koraleen Zucht, Balling, Biopellets, ReefForest and now Triton. I tryed to use ozone, UV, I tryed everything and no success!!!!!

I talked to Triton Brazil today about the N test. They said me that Triton do not do NO3 test, but they do the Nitrogen test, more accurately for them. Triton calculate the NO3 from the Nitrogen test and in Triton opinion, much more accurately than the regular marine NO3 tests. So, I think that we can assume from now a 4ppm value for NO3 in the tank.

I also talked to pipes company and they do not use any kind of anti mold agents in the manufactory.

Rgds,

Daniel

kenchilada · Jan 7, 2021

How did you raise PO4 (I hope via nutrient import and not dosing a chemical)? You said your fish are doing well. How many fish? What, how often, and how much do you feed the tank? I have no experience with a 1300G tank but it must require an incredible amount of food, when I think of how heavily I feed tanks a tenth of this size. Also to feed heavily and then have such low nutrients you must have incredible export. Maybe describing this would help give a better picture of your situation.

Cory · Jan 7, 2021

What kind of salt do you use? Or is it from the sea? Does your city introduce chloramines to the tap water you filter? Whats the tds of your reverse osmosis? Really a strange problem. Have you taken apart all your pumps and checked for rust and swelling plastic? Any algae magnet scrapers left in the tank? Do they spray for pests inside and outside nearby sometimes?

Id be curious of what a metal halide would do for the corals. Maxspect leds arent really super popular anymore. Maybe throw on a metal halide.

Courtney Aldrich · Jan 8, 2021

Hi Daniel,

I'm joining the party late, but wanted to say that I agree the BOD test will be useful to distinguish the type of TOC in your system and answer the prevailing hypothesis that a majority of the TOC is not biodegradable and potentially toxic. I found a paper measuring the impact of bioremediation and ozonation on removal of TOC (see: https://sci-hub.se/10.1016/S0273-1223(99)00652-6) and the efficiency of ozonation is dependent on the type of TOC - higher molecular weight compounds are easier to remove, but no more than 30% of the TOC was removed using ozone levels of 7 mg ozone per ppm of TOC.

There are some chemical methods to distinguish the type of TOC that can at least tell you some basic information about the type of compounds (polar/nonpolar, low/high molecular weight, fluorination) which might be useful. A group in Chile (see: https://www.hindawi.com/journals/jchem/2016/1537370/) published a nice paper analyzing TOC in water using a variety of methods. You might try contacting them to see if they'd be willing to analyze one of your water samples.

Polyfluorinated substances (PFAS) are notoriously toxic, not biodegradable, not destroyed by ozone, nor efficiently removed by carbon. These compounds have been widely used and pose a significant environmental hazard. Your ICP results do not test for fluorine, so you might consider sending your water to another lab for analysis. Seawater seems to be about 1 ppm fluorine.

I'm not an expert on water chemistry having just joined reef2reef (my tank is cycling) and only spent a 30 minutes quickly bringing myself up to speed, so I'm sure there's much better information available.

Courtney

Hans-Werner · Jan 8, 2021

Daniel Almeida Prado said:
A few months ago I increase the level of PO4 to 0.08-0.1. The corals continued to die by the same way, unfortunately!!!

Yes, but you have to improve at least two things at the same time. One is the phosphate and the other is the trace elements. With the conditions now the corals can't survive, obviously.

Changing one thing and leaving the others out of tolerable levels will not help, I believe you. You have 0.01 ppm phosphate, high nitrogen and 0(!) iodine, nickel, zink, molybdenum and so on, all below detection limit.

All organisms need all macro and micro nutrients at the same time and in available forms and concentrations, otherwise they perish.

I just repeat my recommendation, increase phosphate to at least 0.05 ppm and start dosing a good trace elements mix. I am convinced this will help in a short time, at least for first tough corals.

clifg · Jan 8, 2021

Wait how does he have 0 iodine? Couldn't this be a big factor?

Lasse · Jan 8, 2021

Daniel Almeida Prado said:
I also talked to pipes company and they do not use any kind of anti mold agents in the manufactory.

Did you ask about the fittings in your pipes? I suppose there are fittings between the different parts of the pipe system. They can be rubber or plastic fittings. Are they treated (or contain) nitrile?

Sincerely Lasse

Lasse · Jan 8, 2021

Courtney Aldrich said:
Polyfluorinated substances (PFAS) are notoriously toxic, not biodegradable, not destroyed by ozone, nor efficiently removed by carbon. These compounds have been widely used and pose a significant environmental hazard. Your ICP results do not test for fluorine, so you might consider sending your water to another lab for analysis. Seawater seems to be about 1 ppm fluorine.

I can´t leave the pipes or the fittings

This substances is used as anti fire agents. I was not thinking about that - was only concentrated at anti mold agents

Its a possibility.

@Christoph - do you know if there is a possibility that a high fluorine content in the water can indicate that it is these types of polyfluorinated substances in the water?

Sincerely Lasse

Hans-Werner · Jan 8, 2021

clifg said:
Wait how does he have 0 iodine? Couldn't this be a big factor?

Yes, likely, but I see it also as an indicator for the general trace elements status. I guess the tank is generally deprived in trace elements, also those that are more often found at concentrations below detection limits.

Daniel Almeida Prado · Jan 8, 2021

kenchilada said:
How did you raise PO4 (I hope via nutrient import and not dosing a chemical)? You said your fish are doing well. How many fish? What, how often, and how much do you feed the tank? I have no experience with a 1300G tank but it must require an incredible amount of food, when I think of how heavily I feed tanks a tenth of this size. Also to feed heavily and then have such low nutrients you must have incredible export. Maybe describing this would help give a better picture of your situation.

Hello Kenchilada,

I the last years sometimes I raised PO4 increasing the fishes population. Sometimes, I added chemicals in water, but always was very difficlt to increase PO4.

I feed one time a day, frozen food and GVG MIx Sera.

Today I have more less 30 fish. 15 tangs!!!

Rgds,

Daniel

Daniel Almeida Prado · Jan 8, 2021

Cory said:
What kind of salt do you use? Or is it from the sea? Does your city introduce chloramines to the tap water you filter? Whats the tds of your reverse osmosis? Really a strange problem. Have you taken apart all your pumps and checked for rust and swelling plastic? Any algae magnet scrapers left in the tank? Do they spray for pests inside and outside nearby sometimes?

Id be curious of what a metal halide would do for the corals. Maxspect leds arent really super popular anymore. Maybe throw on a metal halide.

Hello Cory,

I use ReefForest Coral Salt. I have an artesian well in my home. I do not have cloramines after the tap water system, but there is an obrigatory cloramine level before my tap water system. I any way, last year I changed the tap water source and start to use another source of tap water that many others reefers used here with success. Nothing change in corals death.

Rgds,

Daniel

Daniel Almeida Prado · Jan 8, 2021

Courtney Aldrich said:
Hi Daniel,

I'm joining the party late, but wanted to say that I agree the BOD test will be useful to distinguish the type of TOC in your system and answer the prevailing hypothesis that a majority of the TOC is not biodegradable and potentially toxic. I found a paper measuring the impact of bioremediation and ozonation on removal of TOC (see: https://sci-hub.se/10.1016/S0273-1223(99)00652-6) and the efficiency of ozonation is dependent on the type of TOC - higher molecular weight compounds are easier to remove, but no more than 30% of the TOC was removed using ozone levels of 7 mg ozone per ppm of TOC.

There are some chemical methods to distinguish the type of TOC that can at least tell you some basic information about the type of compounds (polar/nonpolar, low/high molecular weight, fluorination) which might be useful. A group in Chile (see: https://www.hindawi.com/journals/jchem/2016/1537370/) published a nice paper analyzing TOC in water using a variety of methods. You might try contacting them to see if they'd be willing to analyze one of your water samples.

Polyfluorinated substances (PFAS) are notoriously toxic, not biodegradable, not destroyed by ozone, nor efficiently removed by carbon. These compounds have been widely used and pose a significant environmental hazard. Your ICP results do not test for fluorine, so you might consider sending your water to another lab for analysis. Seawater seems to be about 1 ppm fluorine.

I'm not an expert on water chemistry having just joined reef2reef (my tank is cycling) and only spent a 30 minutes quickly bringing myself up to speed, so I'm sure there's much better information available.

Courtney

Hello Courtney,

Many thanks about the articles. Really, when I used Ozone, nothing got better here, unfortunately.

I will try talk to the Chilene company to check about these tests. I apreciate your help.

I already did other water tests about cloramines and fluorines, but it was regular.

Many thanks for your help.

Rgds,

Daniel

Daniel Almeida Prado · Jan 8, 2021

Hans-Werner said:
Yes, but you have to improve at least two things at the same time. One is the phosphate and the other is the trace elements. With the conditions now the corals can't survive, obviously.

Changing one thing and leaving the others out of tolerable levels will not help, I believe you. You have 0.01 ppm phosphate, high nitrogen and 0(!) iodine, nickel, zink, molybdenum and so on, all below detection limit.

All organisms need all macro and micro nutrients at the same time and in available forms and concentrations, otherwise they perish.

I just repeat my recommendation, increase phosphate to at least 0.05 ppm and start dosing a good trace elements mix. I am convinced this will help in a short time, at least for first tough corals.

Hello Hans,

I agree with about PO4 and trace elements. When I started Triton, I have had dose all of the recommended trace elements from the company and increased PO4. No results.

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.

Rgds,

Daniel

Daniel Almeida Prado · Jan 8, 2021

clifg said:
Wait how does he have 0 iodine? Couldn't this be a big factor?

Clifg,

No. The Iodine is important of course, but not to avoid the corals death like in my reef.

Rgds,

Daniel

Daniel Almeida Prado · Jan 8, 2021

Lasse said:
Did you ask about the fittings in your pipes? I suppose there are fittings between the different parts of the pipe system. They can be rubber or plastic fittings. Are they treated (or contain) nitrile?

Sincerely Lasse

Lasse,

Good point. I didn't ask. I will do this right now.

Rgds,

Daniel

Daniel Almeida Prado · Jan 8, 2021

Lasse said:
I can´t leave the pipes or the fittings This substances is used as anti fire agents. I was not thinking about that - was only concentrated at anti mold agents Its a possibility.

@Christoph - do you know if there is a possibility that a high fluorine content in the water can indicate that it is these types of polyfluorinated substances in the water?

Sincerely Lasse