Vodka, vinegar,biopellets and other organic carbon dosing

[tmz]

Vodka, vinegar, biopellets and other organic carbons.Why dose them? Why not dose them?

There a have been a number of questions on organic carbon dosing and are thousands of posts on the Reef Chemsitry forum. I have many pms on this subject . This thread is intended to help folks who are considering using them. I'll discuss what they do and offer comparisons on various methods for folks to consider. It is a complex subject and much is still unknown but I'll try to avoid being arcane. I'll do it in sections and take questions along the way if you have them.

The goals for organic carbon dosing are: reducing NO3 and PO4 thus allowing tanks to support more bioload and feeding than otherwise; adding bacteria at the bottom of the food web.

Let's start with the bacteria.

The first objective when dosing organic C( carbon) is to proliferate bacteria in the aquarium that will take up inorganic nitrogen(N) and inorganic phosphate(Pi) commonly referred to as NO3/ nitrate and PO4/orthophosphate).

As bacteria multiply, they convert the inorganic N and P ,commonly called nutrients( NO3 and PO4) in the hobby, to organic forms as part of their bodies or as by products.These organics can be consumed in the food chain and/or exported by foam fractionation ( skimming) and/ or adsorbents like granulated activated carbon (GAC). The inorganic N and P can not be exported short of large water changes unless it is converted to an organic form via biological activity by bacteria ,algae,sponges etc. Inorganic N and P do not bind to GAC and are not attractedt o the air water interface which makes them unskimmable.
The bacteria involved in this process are facultative heterotrophic bacteria of various species with dominance related to the type of organic carbon they are breaking down.
Facultative means they flourish in environments with and without oxygen. Taking the free oxygen first as it takes less enrgy for them to do so and then moving on to the oxygen fixed to nitrate( NO3).
Heterotrophic means they need a source of organic carbon(C) since they can't make their own as they are non photosynthetic. Organic carbon is a critical nutrient for all living things along with N and P.. We don' hear about C as much as N and because we can't measure it with hobby grade equipment. There will be more on this in the next section which will be on the nutrients.
The bacteria will use the oxygen in a particular area and when it's gone they start taking it from the NO3; the later process is known as anaerobic respiration. This occurs even in thin bacterial films. Once the bonds between the O3 and N are broken by these bacteria, the resulting N binds to N forming N2( nitrogen gas) which bubbles out of the tank. This adds to the N taken out as food thus depleting additional N from the aquarium. The relative amounts of aerobic( free oxygen consuming ) activity and anaerobic activity will vary from tank to tank spending on a number of variable like surface area,flow etc.


OK, time for a break and some discussion before moving on to the nutrients, alternative carbon sources and a few other things.

 

[Conesus_Kid]

I'm subscribing to this thread. Whether I decide to utilize carbon dosing or not, I know this will be informative. Thanks for sharing your knowledge and experience, Tom! :thumbsup:

 

[Dave VG]

Subscribing as well, been thinking allot about bio pellets lately. Been pretty hard wading through all the BS on RC about them. Thanks for sharing your knowledge with us Tom .

 

[tmz]

Thanks for the replies.
The point of this thread is to provide information about the whole process in a succint way to enable folks to decide if it's a useful method for their situation. It is not to encourage or discourage organic carbon dosing or to pick a particular type . As many know , I have had success with it but there are downsides and accounts of negative experiences. On balance it may not be useful in a number of tanks . However, if done with a good understanding of what's happening and patient moderate dosing it will do no harm and may have significant benefits ,ime.

 

[pascal32]

thank you Tom. Looking forward to future additions to this thread. I've been slowly reading about carbon dosing

 

[filly469075]

thanks tom for the info

 

[TomBONAIRE]

You take a complex subject and boil it down well...thx for the Bio class.

 

[cuch]

Great post very interesting!

 

[Gravesj1s]

Ive been a little hesitant here Tom in that I think I've asked most of my questions directly to you and also feel I have gained a decent amount of knowledge through reading and having the priviledged opportunity to run these topics by you at times.

However I try,there always seems to be that one more question that justa'stumps ya' ...I meant me

Leaping back I did a post not to long ago Re: going beyond dosing.after noticing I was nearing the limit with limewater and you chimed in about spiking a still reservior could yield me roughly a 3o% gain Ca.with a vinegar addition.Along with other obvious benefits you note with N & P reduction.

Around the sametime a thread in the chem forum surfaced and,has had me hmm-in & haw-in, and applying it to limewater spiked with vinegar..is kinda scary.
FWIW- I did reread your response noticing your comment of "bolus dosing"
Im sure you probably figured where Im going with this.

1) Did you choose the bolus dosing partly because of impurities in limewater?
2) -and it doesn't have to be anything scientific ,your"gut feeling " works for me.
Do you think any of us would be setting our selves up for trouble when some of these metals undoubtedly come into solution from adding the vinegar to a still reservior? I didnt see it mentioned in the chem forum or in the article linked here in the forum but, seems a legit question.

Thanks either way Tom,I appreaciate your time here regardless.

-Steve

 

[tmz]

Thanks forthe questions.

1) Did you choose the bolus dosing partly because of impurities in limewater?

No , not at all. I started with bolus dosing of vodka and just carried it to the vinegar too. I don't spike the limewater ,2tsps per gallon covers it for me . It wouldn't effect impurities as they would still drop out. Some folks mix it in the limewater. Also most of my dose is vodka not vinegar . While either can go in the limewater .vokda won't increase calcium chloride saturation limits like vinegar does.
I bolus doe because it gives me a sense of control over the time and amount of dose. Also bolus dosing is thought to increase anaerobic activity as bacteria react in a burst to larger amounts of organics and in so doing may form thicker films with more anaerobic areas.



2) -and it doesn't have to be anything scientific ,your"gut feeling " works for me.
Do you think any of us would be setting our selves up for trouble when some of these metals undoubtedly come into solution from adding the vinegar to a still reservior? I didnt see it mentioned in the chem forum or in the article linked here in the forum but, seems a legit question.

I don't know what metals you mean. If you mean impurities in the calcium hydroxide powder I don't see how they would dissolve in fully saturated limewater with or without vinega;,the ph is still high But I don't dose it that way for the reasons noted. Others do without issues as far as I can tell. Some rely on the ph of the limewater to allow dillution of the vodka or vinegar while continuing to keep keep bacterial degradation at bay.

After I do the nutrient section and alternative carobon source section I'll get into dosing methods i a little more detail.

 

[tmz]

The nutrients:

There are three: C (carbon) , N ( nitrogen) an (P) phosphorus.
They are all formed in large stars. They bring the energy of the universe to life forms. They all cylce .
They are present in oragnic forms( bound to one or more H protons) or inorganic forms.

Carbon is present as CO2 and carbonate ,bicarbonate and carbonic acid in it's inorganic forms. It is also present as organics : polymers I (carbohydrates ), monomers(sugars) ,ethanol, acetic acid et alia. It is essential for life paticularly as organic carbon from photosyntesis which traps the light enegy of the sun in the bonds.
Nitrogen is a abundant as N2 nitrogen gas makes up about 78% of the earth's athmosphere. It is present in organic forms like NH3 and 4 (ammonia),proteins , dna etc or inorganic forms like NO2(nitrite) and NO3(nitrate) .
" Nitrogen is a constituent element of amino acids and thus of proteins and nucleic acids (DNA and RNA). It resides in the chemical structure of almost all neurotransmitters, and is a defining component of alkaloids, biological molecules produced by many organisms. The human body contains about 3% by weight of nitrogen, a larger fraction than all elements save oxygen, carbon, and hydrogen." wikepedia.

Phosphorous is present as inorganic phosphate also called orthophosphate and organically bound forms .
"Phosphorus is essential for life. As phosphate, it is a component of DNA, RNA, ATP, and also the phospholipids that form all cell membranes." Wikepedia.

OK , I'll stop for now . Questions? It's really enough to know these three elements C,N,P are needed by living things and are only useful to life in certain forms and balances. Significant variations can either produce udesireable life forms , like excess cyanobacteria or nusiance algae or create conditions that kill or crash a tank full of invertebrates or fish.Therein lies the challenge, having enough of them( not none as some systems strive for) in the right forms which are changing in the blink of an eye in response to conditions like ph and in the right balance or ratios to meet the needs of the particular organisms in a particular tank.

There will be more on nutrients later today

 

[Gravesj1s]

I don't know what metals you mean. If you mean impurities in the calcium hydroxide powder I don't see how they would dissolve in fully saturated limewater with or without vinega;,the ph is still high

After I do the nutrient section and alternative carobon source section I'll get into dosing methods i a little more detail.

Ok,thanks Tom,and sorry if my question was vague.This should help clarify my concern.
The full article here.

http://reefkeeping.com/issues/2003-04/rhf/feature/index.php

From it,
Exactly how effective this process is at reducing the concentration of metals depends on the metal, the pH, and whether vinegar (and how much) has been used in the limewater (vinegar alters the pH and hence the solubility of many hydroxide species, it also potentially allows for soluble metal acetates to exist in solution). Some metals can form soluble complexes under the conditions present in limewater. Copper, for example, can form the unusual species Cu(OH)3-. It is the solubility of this species, rather than bare Cu++ that limits how effective limewater is at such self-purification.24

Seems to be some wide variations in both CaOH & CaO ,too,with regard to some of these impurities,depending on brand.(ex.-mrs wages pickling lime appears to have a high amount of aluminum.This is also shown in the same article.
Something like 2000ppm if I recall correctly.

I dont want to sidetrack the thread with this,just trying to clarify what I was thinking might be a legit cocern.

Thanks as always,

-Steve

 

[tmz]

Steve, There is no need to be concerned . A lot of vinegar would be needed to drop ph low enough with low dose of kalk to get ph to a point where metal hydroxides would dissolve.. Different metal salts have different solubility points. Some are amphoteric, ie they dissolve at high basicicty or high acicdity.. Getting into details on metals is beyond the scope of this thread. I promised to try not to be arcane. Besides the extra organics could make it easier for any free metals to bind with organics thus alleviating toxicity. I'll talk about dosing methods later including adding vinegar to a still lime water reservoir.

 

[cardiffgiant]

Tom, I'm looking forward to your comments on spiked kalkwasser. I spike mine with about 15ml vinegar/gallon. I've read recommendations of up to 15ml per liter, but have never gone that high myself. I don't think that what I'm adding makes a huge difference for NO3 and PO4, but it seems to be enough to keep my aqua lifter pump and lines from accumulating buildup and clogging.

 

[jim jr]

I add 40 ml of vinegar and 2 teaspoonfuls of kalk to a gallon of ro/ di water and add to my ato , I've done this for about 2 years my nitrates and phosphate is always zero and my corals grow very fast .

 

[pascal32]

Excellent writing Tom.

One of the thoughts on my mind lately is nutrients and the effect on how "good" corals appear in our aquariums. Reflecting on the last few years I'm starting to believe that having sufficient nutrients in a system is vital for corals to flourish - on the other hand i struggle with numerous articles which talk about coral reefs being low nutrient environments. Even more intriguing is that these high bio-load glass cage systems (like yours) maintain low nitrates and phosphates in what I suspect is a nutrient rich environment. In part this is appears to be the result of carbon dosing.

When i see SPS tanks with excellent coloration and growth there always seems to be a medium to large bio-load in the tank (fish). I have seen less tanks that look this good without a significant bio load.

I'm curious as to
(1) the source of N & P (inorganic)
(2) if these are actually in abundance in coral reefs, however are not visible due to the exchanges occurring with symbiotic relationships?
(3) how we can evaluate our level of "nutrient richness" be it direct, or indirect?
(4) how the nitrogen cycle plays into this
(5) is it possible for us [or should we even] consider introducing N and P in low bio-load systems?

sorry if these questions are naive

 

[tmz]

Sorry ,it's taking a while for these installments. It takes time to to think them through and present them succintly. I'm reminded of a famous quote by Mark Twain who at the end of an eloquent and long letter to a friend apologized for the length of the letter explaining that ,if had had more time , he would have written a post card.
I'll get to all the stimulating questions and comments soon but for now a little more work on the framework and foundation may be useful.

So back to nutients and balance for a bit.

There are many unknowns about the process of organic carbon dosing in a reef tank. There are millions of players and complex interactions. There are some things we know and can reasonably extrapolate ; some things that seem at first to be counter intuitive, and; somethings we don't know at all and probly haven't even thought of yet. Confusing it all even more are lot's of pet theories and commercial products for organic carbon dosing or super bacteria with secret proprietary formulae backed by little , no mistated science.

One question that puzzles me is: where does the organic carbon go? Why does dosing it proliferate bacteria ? Since we add organic C,N and P mostly from foods derived from biological matter ,we know it contains C N and P in appropriate proportions for life.
Quantitative assays for most of the seas in the world have been done for C,N and P .The en masse ratio for these elements in sea life has been known since 1934 when the Redfiled ratio was published. There are 116 parts C to 16 parts N to 1 part P.
So when we feed the tank or an organisms decays we get approximately that ratio of C.N and P( individual organisms inculding the bacteria vary a bit but the ratio is a good general measure and gives perspective) .
Further, photosyntetic organisms in a reeftank add more organic C as they produce it as sugars from CO2 ,water and light.
Seems like the heterotrophic bacteria should just keep on truckin until all of the energy in the organic C ,N and P was used up tuning the phosphate to mineral form, the nitrogen to N2 gas and the organic carbon to CO2 , acetate or methane.
If that were the case, there wouldn't be any excess NO3 or PO4 hanging around making trouble. Heterotrophic bacteria of one species or another will use every bit of energy unless they are limited by a lack of organic C or N or P. So if the bacteria stop growing they leave NO3 and PO4 unused which would not happen unless a lack of organic carbon was limiting them.Where does it go?

Perhaps the organic C leaves as CO2 as the sugar is used for energy by living things. Some might be converted to lipids and exported via skimming or stored by the creatures using it. Some might hang around as fulvic and humic sustances which by their refractory nature resist degradation by bacteria. I don't know. I do know that when polymers(carbohydrates) ,monomers( sugars et alia) ,ethanol or acetic acid et alia are added bacteria proliferate and NO3 and PO4 levels drop as these bacteria and their by products which move the NO3 and PO4 back to exportable organic forms are exported via skimming and gac.

The processes involved are known as anaerobic digestion , acetogensis or methanogenis. A cascade of bacterial species degrade carbohydrates( starches, potatoes, rice ,plastic bio pellets, etc) to monomers( sugars like glucose, fructose, siucrose) then others take the monomers to lipids and ethanol ,others take the ethanol (vodka) to acetic acid(vinegar); others to acetate ,and; others to methane. That is an oversimplified summary of the processes. Not all of this occurs in a reef tank. How much does is unknown . BTW ,methane is produced in anoic muck and mire and very deep( 100s of meters ,IIRC,) of sand depth. So I wouldn't worry about blowing up your tank .

 

[tmz]

Nutrtient balance ;

Most are familiar with balances in calcium alkalinity and magnesium but when dealing with nutrients, particulary NO3 and PO4 the common modus operandi seems to be go for 0. The less the better is mostly true but to a point..

Surface reef waters hold very low levels of NO3, around 0.2ppm and PO4 0.005 ppm Green microalges are known to be limited by levels under .03ppm. Deeper more turbid waters where many lps and leathers live hold considerably more. Even in low level areas the available nutrients are constantly available as upwelling through the reef structure keeps them coming
So how do we deal with balance and nutrient levels in a reef tank when we want to keep a variety of invetebrates and maybe a macro algae refugium too?

Invertbrates are usually termed autotrophic/photosynthetic or heterotrophic/non photsynthetic. The truth is almost all of them are mixotrophic and have some variable level of heterotrophic need for organic carbon.. They can not produce all the organic carbon they need from photsynthesis and need some from food or absortion from the water. They also need a relatively constant supply of phospahte and nitrogen. One of the problems with tactics to remove NO3and PO4 is rapid depletion which in some cases occasions significant coral stress and deterioration..
Reefs are full of food constantly. So called ulns( ultra low nutrient systems ,a common term without precise meaning) are not. Go for zero NO3 and PO4 and then add back elements and ammino acids to make up the loss is the way they work. They might be fine for pastel sps and for folks who like to mange lots of supplements and experiment with them. Many folks like thees approaches,( zeovit systems et al) and enjoy the hobby that way. However, I doubt you can keep many lps growing in them for very long.

The need for organic carbon was discussed in the previous section. The same principles apply to nitrogen and phosphorous. If either are absent the bacteria will not grow and the carbon dosed can just build up. Excess organic carbon is harmful and covert since we don't measure it.
Nitrogen defficiencies are commonly reported but are unlikely to occur in a fed tank.

PO4 deficiencies with heavy adsorbent(gfo, aluminum based adsorbents, et al.) or flocculant ( lanthanum chloride) use may also occur even in a fed tank.

A few folks dose KNO3( potassium nitrate) to correct nitrogen deficiencies. Many more use amino acids which contain nitrogen. I imagine some dose PO4 in some form too but don't recall any such accounts. Food and fish waste do fine for both.

 

[tmz]

Should I dose organic carbon?

It depends on your tank and your goals. If the tank supports the life you want in it without high NO3 and PO4 or excessive nuisance algae growth ,then dosing is unnecessary. If you use some PO4 removers, macro algae, etc and don't have a problem with cyano hair algae or high nutrients and are happy with those methods then dosing is probably not right for your tank and routine. If, however , your tank reaches a point where more help is needed to balance the nutrients at low levels and you like to feed your fish , organic carbon dosing is very useful.
The bacterial proliferation boosts the food web from the bottom up too . Some corals like zoanthus thrive with it ,in my 3+ year experience dosing vodka and vinegar.. Sponge growth is also proliferous. Some corals do fine but grow better in higher nutrient tanks; euphyllia caulastrea and some anemones are notable examples.


There are potential downsides. When you dose an organic carbon and bactierial activity accelerates the tank changes in terms of the nutrieints in it,the food web , water clairty and light penetration, and I suspect the organization of the organics and other parametrs. CO2 is produced resulting in some reduction in ph., Metals and other trace elements may also be used in greater quantities or more readily bound to organics which can be a good thing. Overdosing may lead to bacterial blooms and oxygen depletion. Some corals may react badly to certain types of organic carbon dosing like sugars even in low doses. . Most will react negatively if too much of any type is used to soon.

Many are using iorganic carbon dosing in one form or another as it is a very effective control for NO3 and there really aren't many others as easy or inexpensive . Denitrifiers, large heavily lit refugia, or perhaps turf scrubbers are all more difficult ime. Dosing also reduces PO4 but may not take it as far down as desired in a particualr tank. If gfo is or another phospahte remover is still needed for the low range PO4 ,it will be much less than before dosing though .

Total organic carbon buildup may also be a concern.;however, with good skimming and gac use it hasn't had any adverse effects in my tanks.

Here is a little more reading on organics and some potential issues with elevated total organic carbon (TOC) from another post of mine:

Organic carbon is a nutrient. Living things need it along with nitrogen and phosphorous. It comes in with food and from biological activity . Photosynthetic animals make it from water and CO2 and capture the energy, light from the sun, in it.

It takes a myriad of forms from carbohydrates to simple sugars to complex chains of alellopathic compunds. Some of these bind to GAC. We can't measure it with hobby equipment; analyzers used by oceanographers, run in the 50k price range. Elevated total organic carbon (TOC)is thought to adversely effect croal symbionts and has been associated with coral stress and mortality. Folks dose it as vinegar, vodka, sugar or carbohydrates like bio pellets to encourage bacterial growth.

Randy Farely discusses organics in this article:

http://www.reefkeeping.com/issues/2004-10/rhf/index.php

These articles may also be of interest:

By Ken S. Feldman, Kelly M. Maers
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.


http://www.reefkeeping.com/issues/2004-10/rhf/index.php

and Part 2:

http://www.advancedaquarist.com/2008/9/aafeature2/



__________________
Tom


This is a post of mine from a a discussion with a proponent of a new commercialy based pellet like product and Randy H Farely. I'm thowing it in here because it highlights some of the downside issues with excess orgnaic carbon particularly sugars .It's a good segue to the next section where different types of oganic carbon and dosing methods will be discussed. It also provides some extra reading for those so inclined:



what do the monomers do once separated from the polymer shape? poster

Originally Posted by Randy Holmes-Farley
Depends on what monomers we are talking about, but many will be taken up and consumed by bacteria and other organisms.


That's my point. These polymer chains are mostly carbon after all, I wouldn't expect to have many (if any) dangerous monomers floating about. poster

Me
We don't know what the polymers in this product contain nor what byproducts the bacteria consuming them produce. They obviously reduce via bacterial activity and hydrolisis to monomers which are more miscible than the polymers and more likely to diffuse.
Monomers don't have to be exotic to be harmful. Simple sugars when dosed in very small amounts have been associated with cyano growth, coral recision, browning ,bleaching and death in many anecdotal accounts and my own experience. This thread may be of interest to those considering polymer/carbohydrate or monomer/sugar dosing:

http://www.reefcentral.com/forums/sh...hlight=glucose

So, I prefer to dose a carbon source that enters the cascading bacterial activity below monomers, ie, vodka and vinegar in my case ,thus avoiding the sugars and bacterial strains involved at the upper levels for polymers and monomers.

 

[iamwrasseman]

very interesting ,just a tad confusing so i will tag along but i also will be reading everything over just to grasp a higher percentage of this awesome insight !
thanks Tom and also thanks everone for the thoughtful questions