No calcium dosing? Only ALK

Belgian Anthias

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I’m not going to fight you every time trying to explain chemistry to you over and over and over.
It is impossible to form calcium carbonate without consuming alkalinity. The carbonate may be made from CO2, and many organisms do that, but that production must deplete alkalinity by consuming OH- or producing H+, or otherwise performing reactions that will deplete alkalinity.
I do understand the difference between CO2 consumption and carbonate consumption and the resulting effects on alkalinity and pH.
As Halimeda does not use system alkalinity ( carbonate) but CO2 for me it is logical one must take into account the CO2 consumption and its effect on pH. The production of bicarbonate, and precipitation into calcium carbonate within the private environment between cells, will only consume system calcium and CO2, supplied by the surrounding waters, this way removing calcium and no carbonate.
If we measure alkalinity we measure system water alkalinty which is an average of everything what has and is taking place.
The driving force for coral calcification is CO3, for Halimeda phothosynthetic driven calcification it is CO2.
It makes a big difference if the processes take place in a closed and private environment, without depleting system alkalinity, between the cells, as it happens in Halimeda. Of course, the chemistry is the same but it is limited to the provided space, Halimeda calcification uses carbonate first produced only in that little private space by CO2 exchange and consumption for photosynthesis, It is the intention harvesting the cultivated Halimeda removing everything from the system

As far as I know, already in the 60ties it was known Halimeda did it differently but it was not yet known how. Stark and Co conluded: Halimeda opuntia and Halimeda discoidea show a stimulation of incorporation by light as well as a diurnal rhythm under identical conditions of illumination. Both phenomena parallel the rhythm of chloroplast migration within the plant. Calcification is also stimulated by the addition of carbon dioxide. ( which is not the case in corals) Such evidence clearly indicated a light-linked mechanism that could involve photo-synthesis. However other metabolic processes, such as respiration, are also implicated. Aeration alone accelerates calcium incorporation. Nitrogen sources inhibit the incorporation of calcium during the day, indicating that cellular ammonia production is probably not responsible for precipitation. The differential wash-out rates of calcium absorbed during the day compared to those at night support the concept of a 2-step mechanism for calcification. (Stark LM, Almodovar L, Krauss RW. FACTORS AFFECTING THE RATE OF CALCIFICATION IN HALIMEDA OPUNTIA (L.) LAMOUROUX AND HALIMEDA DISCOIDEA DECAISNE(1). J Phycol. 1969;5(4):305-312. doi:10.1111/j.1529-8817.1969.tb02619.x)
Halimeda was commonly used in the seventies, after we changed the filter sandbed for oyster shell grit in our bio-filters , the difference between using Halimeda or Caulerpa was noticed. Also, buffering the water was suddenly not that difficult anymore, and we could not use anymore the decreasing period between the need for buffering the water to decide to do expensive water changes. So water changes became rare. Our guide till then was pH and hardness and the decreasing period it stayed buffered between corrections, till we had the means for measuring the nutrient content later in the seventies.

We then did not know why because we were not chemists. Our only guide was Frank de Graaf.
Frank De Graaf. Handboek voor het tropisch zeeaquarium. Tweede druk. A.J.G. Strengholt N.V. Amsterdam, 1969. And he did explain it correctly, taking into account what was known then. The book, still very useful for learning the basics to a nonchemist, was translated in English Graaf, Frank de. Marine Aquarium Guide. Harrison, N.J.: Pet Library, 1973.

Now we do know why because some people looked for answers and had the means.
Maby it is not correct to speak of system alkalinity consumption based on calcium carbonate consumption in an ongoing changing environment of a closed aquarium system?

Here it is only about managing calcium without effecting system alkalinity much, provide a stable environment without the use of chemicals.

And I am still convinced Halimeda removes calcium without consuming system alkalinity. Doubts? Try it out!
 
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Belgian Anthias

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This linked scientific article which can be read in full for free monitors calcification in various halimeda species under various conditions monitoring the drop in alkalinity:


“Rates of calcification were determined with the alkalinity anomaly technique (Chisholm and Gattuso 1991).”

If you go to that reference, you can see that it is performed by measuring the drop in total alkalinity during calcification:

How calcification is measured. To have correct measurements one has to measure where the action is.
The reference is about coral calcification measurement which of coarse can be based on system alkalinity as they use calcium carbonate based alkalinity for calcification, measurable in the system water. Wich is not the case for Halimeda calcification.
 
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Crusty22

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For the billionth time calcium and alkalinity are not consumed at balanced ratios unless you have a very mature tank and a massive load of hard corals or clams. Alk is consumed in younger tanks via algae and bacteria colonies at an astonishing rate because its biological food. Calcium is consumed at a fraction the rate....unless you have lots of clams or big monitora caps or table acros. A half dozen small SPS frags in a big tank wont budge calcium levels over even months.

The clowns pushing balanced dosing on non SPS dominant tanks arent much better than robo callers selling you car warranties and I really wish Randy would take a stronger stand on this.

Keep your alk stable and slightly elevated on younger tanks. Put your calcium test kit away.

just to clarify, on younger non-sps dominant tanks, you would recommend dosing alk to keep it stable or slightly elevated, and you would recommend to stop dosing calcium if it’s not needed?
what your saying makes since. My alkalinity on a younger tank keeps rapidly dropping and I couldn’t figure out why. Only have a few small sps frags and mostly softies in it.
 

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For the billionth time calcium and alkalinity are not consumed at balanced ratios unless you have a very mature tank and a massive load of hard corals or clams. Alk is consumed in younger tanks via algae and bacteria colonies at an astonishing rate because its biological food. Calcium is consumed at a fraction the rate....unless you have lots of clams or big monitora caps or table acros. A half dozen small SPS frags in a big tank wont budge calcium levels over even months.

The clowns pushing balanced dosing on non SPS dominant tanks arent much better than robo callers selling you car warranties and I really wish Randy would take a stronger stand on this.

Keep your alk stable and slightly elevated on younger tanks. Put your calcium test kit away.
thats a great answer thank you!
 

Belgian Anthias

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A lot of marine algae consume calcium and may contain a lot of it, algae use calcification to manage their CO2 carbon source. HCO3 can be transformed back to CO2 internally. Algae may consume or add alkalinty, it depends also of the nitrogen source used to grow. The consumption of nitrate for algae growth brings back alkalinity but will consume calcium. ( Ref: MB CMF De Haes 2017-2019 Anthias 2020 ) The calcium consumption of algae may be surprisingly high!

If nitrification can take place in a biofilm growing on a substrate of calcium carbonate, nitrification will consume very little or no alk from the system water and calcium is added, enough to compensate for the calcification rate of algae taking up the produced nitrate. In the case produced nitrate is consumed by the algae the water will be buffered.

This way calcium and alk can be managed using AAM.

In the ocean Ions such as Na+, K+, Ca2+, Mg2+, Cl −, SO42−, and NO3− are considered conservative, their presence being little or unaffected by pH, pressure and temperature. Therefore, alkalinity is sometimes seen as the conversions between HCO3− and CO32−. This is NOT the case in the small closed environment of an aquarium! ref: MB CMF De Haes 2017-2019
For example: if 50ppm nitrate is measured this means the alk consumption for the production of 50ppm nitrate was not compensated for but 50 ppm nitrate also represents total alkalinity which is not measured. What happens if alkalinty is corrected without correcting the nitrate level? What about total alkalinity?
 

arking_mark

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Interesting discussion. For the non-chemists, are we saying that Halimeda takes in CO2 and Ca and combines it with H2O to produce CaCO3 and pumps out two H ions?
 

arking_mark

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Interesting discussion. For the non-chemists, are we saying that Halimeda takes in CO2 and Ca and combines it with H2O to produce CaCO3 and pumps out two H ions?


This article, if I understand it correctly, seems to imply that Halimeda may use abiotic precipitation to form CaCO3. It raises the pH locally to precipitate out CaCO3 from the surrounding water. If this is correct, then it takes up Alkalinity and not just Calcium.
 

Belgian Anthias

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This article, if I understand it correctly, seems to imply that Halimeda may use abiotic precipitation to form CaCO3. It raises the pH locally to precipitate out CaCO3 from the surrounding water. If this is correct, then it takes up Alkalinity and not just Calcium.

Calcium is part of total alkalinity, the consumption of calcium in a small closed environment does influence total alkalinity.
In a reef aquarium calcium is not a conservative part of total alkalinity.


In most calcifying algae, calcification occurs extra-cellularly, in direct contact with the surrounding water, whereas in corals the site of calcification is shielded from the seawater by coral tissue although it also takes place outside. The availability of CO3 in the water was found to be the most important factor for the calcification capacity. Only CO2 can be used by RuBisco, which means used HCO3 must be transformed back to CO2 to support respiration (dissimilation).

In Halimeda, calcification occurs in the interutricular spaces that have a diffusive connection via cell walls with seawater. The pH increase due to CO2 consumption is taking place in the small open spaces within the algae, having a huge effect on local alkalinity ( the shift to HCO3 to CO3? ) within the interutricular space, resulting in CO3 availability and CaCO3 formation. Ca and CO2 which is diffused true the cell walls into the interutricular space is used for calcification, driven by a high CO2 demand to support the energy consumption. ref: MB Anthias 2020

Will there be an effect on the transition of HCO3 to CO3 in the system water, effecting measurable alaklinity ? No CO3 already present in the system water is consumed for calcification by Halimeda? HCO3 can be used by algae for respiration after transformation to CO2! Using Halimeda in an algae filter or and AAM and not taking in account the nitrogen source used , will the measurable system alkalinity be depleted due to calcification by Halimeda? I see no reason why!

Using AAM, Halimeda can be used to manage the calcium content, this if to much calcium is produced due to active remineralization taking place on a calcium carbonate containing substrate or and due to using BADES to export nitrogen.


Will there be an effect on the transition of HCO3 to CO3 in the system water effecting measurable alaklinity ? No CO3 already present in the system water is used for calcification? HCO3 can be used by algae for respiration after internal transformation to CO2! Using Halimeda in an algae filter or and AAM and not taking in account the nitrogen source used , will the measurable system alkalinity be depleted due to calcification by Halimeda?

Halimeda can be used to manage the calcium content, this if to much calcium is produced, due to active nitrification taking place on a calcium carbonate containing substrate or and due to using BADES to export nitrogen.
 

arking_mark

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Calcium is part of total alkalinity, the consumption of calcium in a small closed environment does influence total alkalinity.
In a reef aquarium calcium is not a conservative part of total alkalinity.


In most calcifying algae, calcification occurs extra-cellularly, in direct contact with the surrounding water, whereas in corals the site of calcification is shielded from the seawater by coral tissue although it also takes place outside. The availability of CO3 in the water was found to be the most important factor for the calcification capacity. Only CO2 can be used by RuBisco, which means used HCO3 must be transformed back to CO2 to support respiration (dissimilation).

In Halimeda, calcification occurs in the interutricular spaces that have a diffusive connection via cell walls with seawater. The pH increase due to CO2 consumption is taking place in the small open spaces within the algae, having a huge effect on local alkalinity ( the shift to HCO3 to CO3? ) within the interutricular space, resulting in CO3 availability and CaCO3 formation. Ca and CO2 which is diffused true the cell walls into the interutricular space is used for calcification, driven by a high CO2 demand to support the energy consumption. ref: MB Anthias 2020

Will there be an effect on the transition of HCO3 to CO3 in the system water, effecting measurable alaklinity ? No CO3 already present in the system water is consumed for calcification by Halimeda? HCO3 can be used by algae for respiration after transformation to CO2! Using Halimeda in an algae filter or and AAM and not taking in account the nitrogen source used , will the measurable system alkalinity be depleted due to calcification by Halimeda? I see no reason why!

Using AAM, Halimeda can be used to manage the calcium content, this if to much calcium is produced due to active remineralization taking place on a calcium carbonate containing substrate or and due to using BADES to export nitrogen.


Will there be an effect on the transition of HCO3 to CO3 in the system water effecting measurable alaklinity ? No CO3 already present in the system water is used for calcification? HCO3 can be used by algae for respiration after internal transformation to CO2! Using Halimeda in an algae filter or and AAM and not taking in account the nitrogen source used , will the measurable system alkalinity be depleted due to calcification by Halimeda?

Halimeda can be used to manage the calcium content, this if to much calcium is produced, due to active nitrification taking place on a calcium carbonate containing substrate or and due to using BADES to export nitrogen.

You lost me here:

Will there be an effect on the transition of HCO3 to CO3 in the system water, effecting measurable alaklinity ? No CO3 already present in the system water is consumed for calcification by Halimeda? HCO3 can be used by algae for respiration after transformation to CO2! Using Halimeda in an algae filter or and AAM and not taking in account the nitrogen source used , will the measurable system alkalinity be depleted due to calcification by Halimeda? I see no reason why!

Can you simplify the discussion?
 

Belgian Anthias

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You lost me here:

Will there be an effect on the transition of HCO3 to CO3 in the system water, effecting measurable alaklinity ? No CO3 already present in the system water is consumed for calcification by Halimeda? HCO3 can be used by algae for respiration after transformation to CO2! Using Halimeda in an algae filter or and AAM and not taking in account the nitrogen source used , will the measurable system alkalinity be depleted due to calcification by Halimeda? I see no reason why!

Can you simplify the discussion?
Halimeda takes up Ca and CO2 from the system water and transforms it to Ca CO3 within the algae. The transformation from CO2 to HCO3 and CO3 takes place within the algae in an open spaces between cells after Ca and CO2 already has passed cell walls, isolated from the system water. pH and alkalinity is affected within the open spaces between the cell walls, isolated from the system water . ref: MB Anthias 2020
As far as I can see there is no shift from HCO3 to CO3 in the system water due to calcification within Halimeda and which will influences alkalinity measurement using tank water.
Most calcifying algae, shells, corals use HCO3 and CO3 becoming available in the system water influencing alkalinity directly.
My opinion, If nitrate is used as a nitrogen source Halimeda will support total alkalinity and the same time consume calcium.
If nitrate is used for algae growth, alkalinty consumption caused by the nitrification processes is compensated . The water is buffered.
 

Randy Holmes-Farley

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Halimeda takes up Ca and CO2 from the system water and transforms it to Ca CO3 within the algae. The transformation from CO2 to HCO3 and CO3 takes place within the algae in an open spaces between cells after Ca and CO2 already has passed cell walls, isolated from the system water. pH and alkalinity is affected within the open spaces between the cell walls, isolated from the system water . ref: MB Anthias 2020
As far as I can see there is no shift from HCO3 to CO3 in the system water due to calcification within Halimeda and which will influences alkalinity measurement using tank water.
Most calcifying algae, shells, corals use HCO3 and CO3 becoming available in the system water influencing alkalinity directly.
My opinion, If nitrate is used as a nitrogen source Halimeda will support total alkalinity and the same time consume calcium.
If nitrate is used for algae growth, alkalinty consumption caused by the nitrification processes is compensated . The water is buffered.

I don't understand exactly what you are claiming, but calcification by any organism (halimeda, corals, snails, etc.) or abiotic precipitation of calcium carbonate all must consume and reduce alkalinity in the bulk water to an identical extent.

It is also true that nitrate dosing and consumption adds alkalinity. Consumption of nitrate that had previously been made by conversion from ammonia will exactly add back the alkalinity lost when the ammonia was converted to nitrate. Thus, unless you are dosing nitrate, or it is rising or falling, the various processes impacting ammonia and nitrate will not impact alkalinity.
 

Randy Holmes-Farley

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You lost me here:

Will there be an effect on the transition of HCO3 to CO3 in the system water, effecting measurable alaklinity ? No CO3 already present in the system water is consumed for calcification by Halimeda? HCO3 can be used by algae for respiration after transformation to CO2! Using Halimeda in an algae filter or and AAM and not taking in account the nitrogen source used , will the measurable system alkalinity be depleted due to calcification by Halimeda? I see no reason why!

Can you simplify the discussion?

There's nothing special about what Halimeda can with with respect to alkalinity in the bulk water that is different than corals.
 

Belgian Anthias

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I don't understand exactly what you are claiming, but calcification by any organism (halimeda, corals, snails, etc.) or abiotic precipitation of calcium carbonate all must consume and reduce alkalinity in the bulk water to an identical extent.

It is also true that nitrate dosing and consumption adds alkalinity. Consumption of nitrate that had previously been made by conversion from ammonia will exactly add back the alkalinity lost when the ammonia was converted to nitrate. Thus, unless you are dosing nitrate, or it is rising or falling, the various processes impacting ammonia and nitrate will not impact alkalinity.

If I recall it was about removing calcium without effecting system alkalinity much.
As explained, the precipitation of calcium carbonate does NOT take place in contact with the bulk water as is the case by corals, shells, most calcifying algae.
The precipitation of calcium carbonate takes place separated from the bulk water, and will all take place in the small environment where it all happens, the transition back to the bulk water depends of what can pass the cell membranes in the opposite direction. From the bulk water only calcium and CO2 is used ( before it turned into HCO3).,Will the alkalinity consumption retrieved from the bulk water be of the same extend as in the case of coral calcification? In Halimeda most of the CO2 production of the calcification process is not released back in the bulk water but is all used.

Following your explanation if 1 gram of calcium carbonate is made by coral calcification or 1gram of calcium carbonate is stored into Halimeda, consumption and reduction of measured alkalinty in the bulk water is to an identical extend. In both cases I have to add the same amount of CO3?
In that case I am wrong and Halimeda can not be used for lowering the calcium content without consuming system alkalinity.


 

Randy Holmes-Farley

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Following your explanation if 1 gram of calcium carbonate is made by coral calcification or 1gram of calcium carbonate is stored into Halimeda, consumption and reduction of measured alkalinty in the bulk water is to an identical extend. In both cases I have to add the same amount of CO3?

Yes, that would be the case.

Whether the organism involved gets the carbon for the carbonate from CO2, bicarbonate, or carbonate from the water, the depletion of alkalinity in the bulk water is the same.

If it takes up carbonate and deposits calcium carbonate, then it obviously depletes alk by lowering carbonate.

If it takes up bicarbonate and deposits calcium carbonate, then it obviously depletes alk, then it depletes alk by consuming bicarbonate and also excreting one H+ (it cannot just "hold" protons inside it):

HCO3- --> CO3-- + H+

If it takes up CO2 and deposits calcium carbonate, then it depletes alk by excreting two H+ (it cannot just "hold" protons inside it):

CO2 = H2CO3 --> CO3-- + 2H+
 

Belgian Anthias

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Yes, that would be the case.

Whether the organism involved gets the carbon for the carbonate from CO2, bicarbonate, or carbonate from the water, the depletion of alkalinity in the bulk water is the same.

If it takes up carbonate and deposits calcium carbonate, then it obviously depletes alk by lowering carbonate.

If it takes up bicarbonate and deposits calcium carbonate, then it obviously depletes alk, then it depletes alk by consuming bicarbonate and also excreting one H+ (it cannot just "hold" protons inside it):

HCO3- --> CO3-- + H+

If it takes up CO2 and deposits calcium carbonate, then it depletes alk by excreting two H+ (it cannot just "hold" protons inside it):

CO2 = H2CO3 --> CO3-- + 2H+
I thought these protons are used to produce CO2 for Photosynthesis 2H+ + 2 HCO3- = 2 CO2 +2H20 . i thought it is the reason why the algae uses calcification this way.
In the inter-utricular space pH is kept very high due to the high CO2 demand and calcium is over saturated.
In Halimeda the calcium carbonate production is completely in function of the CO2 needs for Photosynthesis , calcification does not take place in direct contact with the bulk water. My opinion most produced H+ ions are well used , not being able to have much influence on the situation in the bulk water.
If Photosynthesis is high the release of CO2 in the immediate environment may fulfill the needs for CO2 used for calcification in the inter-utricular space. A fine self supporting system based on calcification.

What will happen if I use a CO2 calcium carbonate reactor to compensate for the effects of calcification by Halimeda?
 

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I thought these protons are used to produce CO2 for Photosynthesis 2H+ + 2 HCO3- = 2 CO2 +2H20 . i thought it is the reason why the algae uses calcification this way.
In the inter-utricular space pH is kept very high due to the high CO2 demand and calcium is over saturated.
In Halimeda the calcium carbonate production is completely in function of the CO2 needs for Photosynthesis , calcification does not take place in direct contact with the bulk water. My opinion most produced H+ ions are well used , not being able to have much influence on the situation in the bulk water.
If Photosynthesis is high the release of CO2 in the immediate environment may fulfill the needs for CO2 used for calcification in the inter-utricular space. A fine self supporting system based on calcification.

What will happen if I use a CO2 calcium carbonate reactor to compensate for the effects of calcification by Halimeda?

No, there is no possible system that results in calcification without consumption of alkalinity from the bulk water. One may couple to it other processes that provide that alkalinity, such as the consumption of nitrate, but nothing entirely internal can do it.

If they use the process you posted above to use up the generated protons, then they must be consuming the bicarbonate that is also in that process, and consumption of bicarbonate lowers alkalinity.:

2H+ + 2 HCO3- --> 2 CO2 +2H20
 

Belgian Anthias

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No, there is no possible system that results in calcification without consumption of alkalinity from the bulk water. One may couple to it other processes that provide that alkalinity, such as the consumption of nitrate, but nothing entirely internal can do it.

If they use the process you posted above to use up the generated protons, then they must be consuming the bicarbonate that is also in that process, and consumption of bicarbonate lowers alkalinity.:

2H+ + 2 HCO3- --> 2 CO2 +2H20
Yes, of course, If calcification takes place in contact with the bulk as is the case by corals ?
CO2 is retrieved from the bulk , HCO3 is not able to pass cell membranes without being broken by certain enzymes.
How it will affect the bulk water as produced H+ ions are not retrieved from bulk water and will not leave the algae, and are reused to become water again. Ions from water within the utricular space are used to produce HCO3 and CO3 within the algae, after calcification the produced ions are given back to make water to provide the CO2 source for Photosynthesis, all without leaving the algae. . What do I have to correct in the bulk as the algae has corrected it already? The same time calcium is stored.
Chemics are not able to split water and gain energy, Bio-chemical processes do it since a very long time.
 

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