Has Anyone tried Tropic Marin Bio-Calcium or Carbo-Calcium

[Randy Holmes-Farley]

This is interesting. May be unrelated but I wonder if this is what I'm seeing when I switched over to AFR. I was originally dosing ESV 2 part and came across the AFR recipe. I thought it looked fun to make so wanted to try it out. Love the stuff. Anyway using the 2 part I was able to keep my ALK pretty steady at 8.1 - 8.3. After switching and starting the initial dose using TM's calculator my ALK dropped steadily every couple days. I increased AFR and then it started to climb so I backed it off. Started to drop again so I started to dose 2 - 3 ml of alk daily over 24 hours. Now it seems to be a bit more back to normal.

So in my case similar to what you said by using another product to keep alk steady in my case. It very well could be that I do not have ARF at the proper dose yet. Is at least my guess.

I'm still skeptical of the whole idea that alk won't rise with overdose, and that formate accumulates substantially, but if true, it really seems to make this product less easy to figure out and control dosing than any ordinary alkalinity maintenance method.

I certainly agree that any balanced product used to boost alkalinity will also raise calcium. CaCO3/CO2 reactors, limewater/kalkwasser, two parts when both are used, and All for Reef. They will all will boost calcium by about 6-7 ppm of calcium for each 1.0 dKH of alkalinity, but that is typically not a concern if the goal is to boost alkalinity by a few dKH.

The relative math does mean that none of these methods are good for boosting calcium since alkalinity will generally get too high, and hence the need to use calcium chloride or just the calcium part of a two part for that purpose.

 

[Lou Ekus]

I'm still skeptical of the whole idea that alk won't rise with overdose, and that formate accumulates substantially, but if true, it really seems to make this product less easy to figure out and control dosing than any ordinary alkalinity maintenance method.

I certainly agree that any balanced product used to boost alkalinity will also raise calcium. CaCO3/CO2 reactors, limewater/kalkwasser, two parts when both are used, and All for Reef. They will all will boost calcium by about 6-7 ppm of calcium for each 1.0 dKH of alkalinity, but that is typically not a concern if the goal is to boost alkalinity by a few dKH.

The relative math does mean that none of these methods are good for boosting calcium since alkalinity will generally get too high, and hence the need to use calcium chloride or just the calcium part of a two part for that purpose.

While I agree with most of your post in relation to these kinds of products in general, I strongly dissagree with the statement that "it really seems to make this product less easy to figure out and control dosing than any ordinary alkalinity maintenance method."

The application is quite simple...if your alkalinity is dropping, from the current dosing amount of formate, then you use some bicarbonate to bring alkalinity back up to the desired value, and slightly increase your dose of formate. That will most likely stabilize the alkalinity. If it did not, and the uptake is even greater than that, then you repeat the process.

If you find there is an ongoing imbalance between the Ca and alklainity uptake, that is not controlled by the formate alone, then a periodic addition, of a small amount of either calcium cholride or sodium bicarbonate will make up that difference. In the vast majority of cases, this is not even necessary.

The ease and simplicity of a single solution, for maintaining these parameters, is hard to beat!

 

[User1]

While I agree with most of your post in relation to these kinds of products in general, I strongly dissagree with the statement that "it really seems to make this product less easy to figure out and control dosing than any ordinary alkalinity maintenance method."

The application is quite simple...if your alkalinity is dropping, from the current dosing amount of formate, then you use some bicarbonate to bring alkalinity back up to the desired value, and slightly increase your dose of formate. That will most likely stabilize the alkalinity. If it did not, and the uptake is even greater than that, then you repeat the process.

If you find there is an ongoing imbalance between the Ca and alklainity uptake, that is not controlled by the formate alone, then a periodic addition, of a small amount of either calcium cholride or sodium bicarbonate will make up that difference. In the vast majority of cases, this is not even necessary.

The ease and simplicity of a single solution, for maintaining these parameters, is hard to beat!

Thanks Randy for your reply.

Lou - thank you also. If it is OK I wanted to ask a follow up question. Using the AFR calculator I put in 210 gallons and it says to start with 39.74 ml per day. That is probably a good number to start with since I'm sure total water volume is less due to rock and sand.

Anyway I have kept my tank at or around 8.1 - 8.4 alk. It seems to be the number it stays at or likes probably due to the current salt (I/O reef crystals). I started AFR at 39 ml a day and slowly increased as I was seeing my alk drop closer to 7.9. I'm now at 45 ml / day. I noticed it was still dropping, slowly over a week, so now dosing 5 ml of esv 2 part (alk only) to maintain it.

Question. Should I continue to increase the daily AFR slightly until I can stop the other ALK addition, or lower it, until it is no longer necessary? Or, do you make the ARF DIY recipe a bit stronger as another option.

In either case my tank is still maturing (2 years) but like the idea of a single dose. Thanks again. A lot of good information in here.

 

[Lou Ekus]

Thanks Randy for your reply.

Lou - thank you also. If it is OK I wanted to ask a follow up question. Using the AFR calculator I put in 210 gallons and it says to start with 39.74 ml per day. That is probably a good number to start with since I'm sure total water volume is less due to rock and sand.

Anyway I have kept my tank at or around 8.1 - 8.4 alk. It seems to be the number it stays at or likes probably due to the current salt (I/O reef crystals). I started AFR at 39 ml a day and slowly increased as I was seeing my alk drop closer to 7.9. I'm not at 45 ml / day. I noticed it was still dropping, slowly over a week, so now dosing 5 ml of esv 2 part (alk only) to maintain it.

Question. Should I continue to increase the daily AFR slightly until I can stop the other ALK addition, or lower it, until it is no longer necessary? Or, do you make the ARF DIY recipe a bit stronger as another option.

In either case my tank is still maturing (2 years) but like the idea of a single dose. Thanks again. A lot of good information in here.

You got it. You said one possibility would be to " continue to increase the daily AFR slightly until I can stop the other ALK addition, or lower it, until it is no longer necessary". That is exactly the right approach. It sounds like you are really close. But might just need a little bit more AFR. The amount that is needed is always related to the population and parameters of each individual system. It sounds like you almost have yours figured out! Let me know if you have other questions.

 

[User1]

You got it. You said one possibility would be to " continue to increase the daily AFR slightly until I can stop the other ALK addition, or lower it, until it is no longer necessary". That is exactly the right approach. It sounds like you are really close. But might just need a little bit more AFR. The amount that is needed is always related to the population and parameters of each individual system. It sounds like you almost have yours figured out! Let me know if you have other questions.

Thank you. Have a great day!

 

[Randy Holmes-Farley]

While I agree with most of your post in relation to these kinds of products in general, I strongly dissagree with the statement that "it really seems to make this product less easy to figure out and control dosing than any ordinary alkalinity maintenance method."

The application is quite simple...if your alkalinity is dropping, from the current dosing amount of formate, then you use some bicarbonate to bring alkalinity back up to the desired value, and slightly increase your dose of formate. That will most likely stabilize the alkalinity. If it did not, and the uptake is even greater than that, then you repeat the process.

If you find there is an ongoing imbalance between the Ca and alklainity uptake, that is not controlled by the formate alone, then a periodic addition, of a small amount of either calcium cholride or sodium bicarbonate will make up that difference. In the vast majority of cases, this is not even necessary.

The ease and simplicity of a single solution, for maintaining these parameters, is hard to beat!

Hmmm. That doesn't sound nearly as simple as dose to your alk target, but let's look at another likely scenario that is much more problematic..

I am dosing All for Reef and measured alk is fine at 8 dKH.

Am I over-dosing the formate? Is formate accumulating?

How would I know? By rising calcium? Seems a very poor way to judge.

If I am overdosing by 1 dKH per day, calcium will only rise by about 7 ppm per day. Against the backdrop of typical water changes and the inherently poor ability to exactly measure calcium, how long would it take to see that difference? A day? (unlikely) a week? (mavbe) longer? (maybe).

How frequent of calcium testing do I need to do to effectively monitor calcium for a potential formate accumulation?

If I am overdosing by 1 dKh (0.4 meq/L) per day, that is a lot of formate (5 ppm C per day). In only a day or two, formate will dominate all other organics in the water put together by a huge margin (the link below suggests total organic carbon in a reef is on the order of 1 ppm).

Total Organic Carbon (TOC) and the Reef Aquarium: an Initial Survey, Part I

Department of Chemistry, The Pennsylvania State University, University Park, PA 16802. Ken and Kelly report on their work on Total Organic Carbon and how it relates to the reef aquarium.

reefs.com

Thus, the potential for formate to be a huge component of the bulk water seems almost unavoidable under the scenario that it might not be metabolized by bacteria (which, again, seems highly unlikely to me to be sustainable long term).

Asked differently, one would be providing a food for bacteria that are certainly known to be able to consume it.

Why wouldn't they expand in numbers to be able to do so?

I'd have to say this thread is making me lose my initial confidence that this product is a good way to go.

 

[Randy Holmes-Farley]

You got it. You said one possibility would be to " continue to increase the daily AFR slightly until I can stop the other ALK addition, or lower it, until it is no longer necessary". That is exactly the right approach. It sounds like you are really close. But might just need a little bit more AFR. The amount that is needed is always related to the population and parameters of each individual system. It sounds like you almost have yours figured out! Let me know if you have other questions.

That constant need to be varying the dose to see if one is dosing just the bare minimum of product necessary to maintain alkalinity seems very tedious relative to simple measuring of alkalinity as one would do with a normal alk product.

This need (if real) is convincing me this isn't a good method for anyone not wanting to be constantly measuring and jiggering doses up and down to see if the dose was optimal or not.

 

[Stoney]

I just switched one of my tanks from BRS pharma to carbocalcium w/ bio mag. So far it's working pretty well. Alk, cal, and mag are all holding steady. However, there's definitely a significant increase in surface film and I had to nearly double my dose of NO3/PO4 to maintain previous levels. Isn't this carbon dosing effect evidence that formate is being metabolized by bacteria, at least to a certain extent? I also noticed the crystallization at the tip of the dosing line, but halving the concentration seems to have fixed the problem.

On an unrelated note, does anyone know if it's safe to add soda ash or sodium bicarbonate to carbo calcium? For some reason most of my tanks consume slightly more alkalinity than calcium and I was thinking I could add soda ash to carbo calcium to precipitate into calcium carbonate and slightly reduce the calcium levels. Is there any reason this wouldn't work? Or is there a better way to achieve this?

 

[Lou Ekus]

Hmmm. That doesn't sound nearly as simple as dose to your alk target, but let's look at another likely scenario that is much more problematic..

I am dosing All for Reef and measured alk is fine at 8 dKH.

Am I over-dosing the formate? Is formate accumulating?

How would I know? By rising calcium? Seems a very poor way to judge.

If I am overdosing by 1 dKH per day, calcium will only rise by about 7 ppm per day. Against the backdrop of typical water changes and the inherently poor ability to exactly measure calcium, how long would it take to see that difference? A day? (unlikely) a week? (mavbe) longer? (maybe).

How frequent of calcium testing do I need to do to effectively monitor calcium for a potential formate accumulation?

If I am overdosing by 1 dKh (0.4 meq/L) per day, that is a lot of formate (5 ppm C per day). In only a day or two, formate will dominate all other organics in the water put together by a huge margin (the link below suggests total organic carbon in a reef is on the order of 1 ppm).

Total Organic Carbon (TOC) and the Reef Aquarium: an Initial Survey, Part I

Department of Chemistry, The Pennsylvania State University, University Park, PA 16802. Ken and Kelly report on their work on Total Organic Carbon and how it relates to the reef aquarium.

reefs.com

Thus, the potential for formate to be a huge component of the bulk water seems almost unavoidable under the scenario that it might not be metabolized by bacteria (which, again, seems highly unlikely to me to be sustainable long term).

Asked differently, one would be providing a food for bacteria that are certainly known to be able to consume it.

Why wouldn't they expand in numbers to be able to do so?

I'd have to say this thread is making me lose my initial confidence that this product is a good way to go.

I am not a chemist, I don't claim to be one, so once we get into the molecular specifics, my knowledge base fails me. So in deference to that, I will say this...

I think this is a really good example of how "bench chemistry" does not always translate precisely into tank chemistry. It is very easy to "over think" the evaluation of the process. With both of these products (Cabocalcium and All-For-Reef) being so popular right now, both here in the US and around the world as well, we have thousands of aquarists using them. Some dosing more, some dosing less. We are still learning about the exact process of the metabolization of the formate into carbonates. We are not seeing any of the issues you are highlighting coming up.

I don't see the huge difference in difficulty in dosing methodologies. It just doesn't seem that difficult to me. But that is just me. If you need more formate to maintain your alkalinity, you bring the alkalinity up and add more. If you Ca is rising too much, you add less. It's just not that complicated.

If you see these differences as huge and untenable, then you would chose to use something else. But many aquarists are finding this extremely easy, effective and convenient. It may end up revolutionizing the methodology of calcium/alkalinity supplementation going forward. Due to my lack of professional chemistry background, I will leave further comment to my team in Germany. They may be able to address your concerns better than I.

 

[Lou Ekus]

I just switched one of my tanks from BRS pharma to carbocalcium w/ bio mag. So far it's working pretty well. Alk, cal, and mag are all holding steady. However, there's definitely a significant increase in surface film and I had to nearly double my dose of NO3/PO4 to maintain previous levels. Isn't this carbon dosing effect evidence that formate is being metabolized by bacteria, at least to a certain extent? I also noticed the crystallization at the tip of the dosing line, but halving the concentration seems to have fixed the problem.

On an unrelated note, does anyone know if it's safe to add soda ash or sodium bicarbonate to carbo calcium? For some reason most of my tanks consume slightly more alkalinity than calcium and I was thinking I could add soda ash to carbo calcium to precipitate into calcium carbonate and slightly reduce the calcium levels. Is there any reason this wouldn't work? Or is there a better way to achieve this?

I've asked our lab in Germany to chime in on this. I don't know if you can add carbonates to the Carbocalcium or not.

 

[hart24601]

Randy I just switched to the (somewhat) DIY all for reef from your hydroxide 2 part. Now I am concerned if you have worries since you are, well Randy! What would I look out in regards to your concerns?

 

[Rybren]

I switched from using Kalk to carbocalcium on my 12+ year old 120G mixed reef about 6 months or so ago. I dose ~26ml per day, broken into 24 doses, every hour, on the hour.

Here are my observations:

1. Alk has remained steady at 8.0+/- 0.1 dKH (using Salifert)
2. Calcium has remained steady at 490 ppm (using Salifert)
3. I had to stop my DIY NOPOX because nitrates became undetectable (using Salifert). After stopping the NOPOX, my nitrates returned to 2.5 to 5, depending on how much I'm at home (I feed 3-5x a day when I'm home)

I am very happy with the carbocalcium dosing regime. The powdered form is very cost effective for me and my alk and Ca numbers are more stable than they were with dosing kalk in the ATO.

 

[Hans-Werner]

In this discussion one aspect was not taken into consideration yet: It is the trace elements All-For-Reef and the DIY recipe contains. I think these make a big difference to a simple two or three part additive.

I think the last two decades of trace element discussion where very much characterized by the Shimek articles, and trace metals in general where characterized as "toxic". Nothing could be further from truth for the biological or essential trace metals. This is why I will call the biological trace elements micronutrients in the following.

A deficiency of micronutrients limits calcification and growth of corals, coralline algae and other organisms. I am convinced and I even know from evidence that growth in many reef tanks is limited by micronutrients. You can see it when alkalinity and the macronutrients phosphate and nitrate start to drop after you have started to add micronutrients. Both has been reported after starting dosing of All-For-Reef.

Some reef aquarists suspect that All-For-Reef lowers nutrients by the addition of organic carbon. This may be the case but it is only part of the truth and in my opinion the smaller part of the truth. I have used the same micronutrients before with the Balling method and have seen no big difference in nitrate and phosphate concentrations, but they have been very low and growth limiting in our tanks anyway, so no much chance to drop much. However the limitation didn't seem to get more severe as should be the case with normal organic carbon dosing for bacterial growth, when bacteria compete with corals for nutrients.

From my experience with micronutrients during the last 2 1/2 decades I know that the effect of micronutrients should not be underestimated. It will alter the processes in reef tanks significantly. Coral growth will be increased, alkalinity, phosphate and nitrate may drop and corals probably will not tolerate alkalinities of 8 dKH and higher at low phosphate concentrations any more. This is what you may observe in more tanks when they start to dose micronutrients.

So a little bit All-For-Reef brought trace metals back into reef aquaria like a Trojan Horse, by the success of a product you did not think much about what is in it. In my opinion micronutrients are an important key to further success in reef aquarium care, and I hope this will alter and revive the discussion about trace metals, especially now that we have the possibility of quite cheap ICP-OES analysis.

We do not know with scientific precision which processes finally lead to some observations we make when dosing All-For-Reef or some other products. Some products and some processes are too complex to judge from external oberservation and simple analytics.

Randy may be right when he says that there is no reason formate should accumulate and prevent alkalinity from rising. Most of the observations of dropping alkalinities and alkalinities not rising as calculated and expected may indeed be caused by the micronutrients and enhanced growth of corals, coralline algae and other calcifying organisms.

 

[Randy Holmes-Farley]

I am not a chemist, I don't claim to be one, so once we get into the molecular specifics, my knowledge base fails me. So in deference to that, I will say this...

I think this is a really good example of how "bench chemistry" does not always translate precisely into tank chemistry. It is very easy to "over think" the evaluation of the process. With both of these products (Cabocalcium and All-For-Reef) being so popular right now, both here in the US and around the world as well, we have thousands of aquarists using them. Some dosing more, some dosing less. We are still learning about the exact process of the metabolization of the formate into carbonates. We are not seeing any of the issues you are highlighting coming up.

Which means that the claim that formate is not being metabolized by organisms other than corals consuming it for calcification is likely not true in real reef tanks. My concern is simple logic based on your claim that one cannot measure the alkalinity that is dosed), not some sort of theoretical chemistry that folks might dismiss.

 

[Randy Holmes-Farley]

Randy I just switched to the (somewhat) DIY all for reef from your hydroxide 2 part. Now I am concerned if you have worries since you are, well Randy! What would I look out in regards to your concerns?

If you want to use the formate products (which won't boost pH but otherwise are likely fine) then I say go ahead and try it.

I do not simply accept the Tropic Marin claim that the formate will accumulate long term if dose at any level higher than the exact coral calcification rate. It is that claim that most concerns me. If true, it is an issue. if not true, there is no issue.

 

[Randy Holmes-Farley]

This article shows that a collection of baterioplankton from the sargasso sea will oxidize formate at formate concentrations much, much lower than we are talking about here:

One Carbon Metabolism in SAR11 Pelagic Marine Bacteria

The SAR11 Alphaproteobacteria are the most abundant heterotrophs in the oceans and are believed to play a major role in mineralizing marine dissolved organic carbon. Their genomes are among the smallest known for free-living heterotrophic cells, raising ...

www.ncbi.nlm.nih.gov

For field studies of radiolabeled compound utilization by bacterioplankton in the western Sargasso Sea, seawater was collected from 10 m at Bermuda Hydrostation S using Niskin bottles, and transferred to an acid-washed, autoclaved polycarbonate carboy. For each experiment, microbial plankton were concentrated from 80 L seawater by tangential flow filtration to a final volume of 600 mL, and isotopic labeling was carried out as described above. The concentrations of the tested compounds were 3 µM glucose, 1.7 µM pyruvate, 0.3 µM formate, 1.1 µM formaldehyde, 50 µM methanol and 0.5 µM TMAO.

0.3 uM formate is 14 ug/L or 0.014 ppm. We are talking about dosing multi ppm levels each day.

 

[Hans-Werner]

Thank you very much, Randy, Pelagibacter ubique ("freewater-bacterium present everywhere"), the name says it all!

I think this supports my explanation that dropping or lower than expected alkalinities are most likely caused by increased growth and consumption.

Nevertheless the coral holobiont is a site of especially high bacterial activity due to the availability of nutrients and other benefits the bacteria get from their animal and algal partners.

 

[hart24601]

Randy, my apologies if this has been asked before, but I was unable to find it. If I am adding 1dkh/day in 100g of formate, what is that equivalent carbon dose of vinegar and vodka? I had been dosing vodka in small amounts not for nutrient reduction but for filter feeder food (which it works great) so I am curious the formate carbon amount.

 

[Hans-Werner]

I am not Randy but I think I can calculate this for you:
100 US-gal. is 378.5 liters
to increase alkalinity by 1 dKH you need 378.5 dKH
The description says 140 gram of Carbo-Calcium Powder contain 6,000 dKH
To add an alkalinity of 378.5 dKH you need 378.5/6,000 x 140 gram = 8.8 gram of Carbo-Calcium Powder or 378.5/6,000 x 1 liter of the solution = 0.063 liter or 63 ml of solution.
8.8 gram of calcium formate is 8.8 g/130.1 g/mol = 0.0677 mol.
For comparison I recommend the caloric value, the amount of energy that can be released by the oxidation of a substance. For availability reasons I will calculate with the caloric value of formic acid. 1 mol of calcium formate contains 2 mol of formate.
1mol of formic acid has a caloric value of 254.6 kJ/mol; This means calcium formate has a caloric value of nearly 509.2 kJ/mol. 0.0677 mol has a caloric value of 34.47 kJ.
Ethanol has a caloric value of 1371 kJ/mol, a density of 789 g/l and a molar mass of 46.07 g/mol.
1 l of ethanol has 789 g*l-1/46.07 g*mol-1 = 17.126 mol/l with a caloric value of 17.126 mol/l * 1371 kJ/mol = 23,480 kJ/l.
1 ml of pure ethanol has a caloric value of 23.48 kJ which is nearly the same as from 23.48 kJ/34.47 kJ*dKH-1 = 0.681 dKH in 100 US-gal. or 0.681 * 8.8 g Carbo-Calcium Powder = 6 g of Carbo-Calcium Powder or 43 ml of the solution.
1 dKH in 100 US-gal., 8.8 gram of Carbo-Calcium Powder or 63 ml of the solution have nearly the same caloric value as 1.47 ml of pure ethanol.

Now you only have to look how much volume-% your vodka has. If it has for example 40 vol-% of ethanol you need 3.675 ml of vodka to dose 1.47 ml of pure ethanol. 3.675 ml of vodka 40 vol-% have the same caloric value in your 100 US-gal. tank as an increase by 1 dKH with Carbo-Calcium or All-For-Reef.

Was anybody able to follow my complete calculations? Was everything correct?

If eveything was correct this shows that formic acid or formate is really a bad energy source for bacteria. This is because 1 mol = 46.025 g of formic acid has a caloric value of only 254.6 kJ which is quite low. Ethanol with nearly the same molar mass has 5.4-fold the caloric value.

 

[Hans-Werner]

*I just have seen, the correct expression would be calorific value instead of caloric value. Please excuse my Germlish!