# Using ascorbic acid to bring pH level down in sugar water



## barberberryfarm (Feb 16, 2013)

I'm planning ahead for when I possibly have to start feeding in the winter. Hopefully, I've left enough honey for them to make it through their first winter, but only time will tell. If I have to, do any of you add ascorbic acid to bring down your sugar water's pH to around 4.5 which would be similar to that of honey? If so, what affects, positive or negative, have you seen? 

Here's a discussion brought up earlier on BeeSource which got me thinking about this. Please pay close attention to Michael Bush's comments as that's what triggered my question - http://www.beesource.com/forums/sho...ling-with-a-HiveTop-Feeder&highlight=ascorbic


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## JWChesnut (Jul 31, 2013)

Some sugar chemistry:
Ascorbic acid is a Carbon ring very similar to Glucose/Fructose. Its molecular formula is C6-H8-O6 (Fructose and Glucose are C6-H12-O6).
Ascorbic acid looks like: 









Please note the hydroxyl (OH-) groups balancing the carbon ring formation. When added to make a solution in water, the following reaction occurs:









In this reaction, the molecule sheds protons (i.e. H+ charged ions), and the ring restabilizes with O-- double bonds to the Carbon. The molecule is the "congugate base" of the ascorbic acid and the two forms exist in equilibrium in water solution. I've drawn arrows showing the escape of these H+ ions.

Ascorbic acid is an acid because it is a proton donor (i.e. it very easily sheds charged H+ ions into the solution). pH is simply a measure of the relative abundance of H+ expressed in negative logarithmn. pH -5 means on a "molecule count" basis there are 1 x 10-5 loose H+ ions in the water. Neutral reaction (pH 7) means there 2 orders of magnitude less (1 x 10-7) loose H+.

Now sucrose's formula is C12 - H22 - O11. This means on a "atom count" basis you need to add 2 H+ and one O-- to sucrose in order to evenly divide it into one Glucose and one Fructose. H2++0-- is of course Water, but hydrolysis (the addition of H+ and balancing OH-) to sucrose does not happen quickly in neutral water. Raising the abundance of "hungry" H+ in the solution speeds the reaction (as does heat, or an enzyme invertase). Honeybees use the enzyme invertase to convert nectar sucrose to the 6 Carbon glucose/fructose pair. The metabolic cost to the honeybee of the hydrolysis reaction is minimal (enzymes are energetically efficient), but the* bees require a molecule of water for every sucrose molecule they split*. This means the "brix" of converted nectar jumps from the concentration at collection to double at storage in cells (even as raw processed syrup). A whole sucrose heavy solution might impose a moisture impact on a hive unable to gather H2O for conversion purposes (I don't know if this has been studied).

Finally, lets look at the process with which the sub-molecules (glucose/fructose) restabilize.








When sucrose hydrolyzes, the intermediate structure are two broken rings or chains. These restabilize into complete rings -- the H+ proton moves off the OH- group at the tail, the now free O-- atom forms a stable bond with two carbons nearby, and the H+ proton moves in (and out) of solution at the O-- tail (which was the atom linking the two halves of the Sucrose structure). This means fructose is a H+ donor to the solution. It acidifies the solution. 

Very little acid needs to be added to a sucrose solution, because the hydrolysis reaction (the splitting of sucrose) generates fructose which is itself a "proton donor"-- and the reaction proceeds on its own reaction product. Honey is low pH because it has fructose in the solution, not because you must lower the pH externally. The pH change is initiated by 1) adding a little acid to cascade the reaction, 2) heating the solution to add "energy" and break bonds, 3) allowing the honeybees to use their invertase enzyme to convert the sugars. The end result is the same.

Honey bees are able to produce ascorbic acid. Likely a bacteria in their gut actual makes the molecule. So Ascorbic is not a vitamin per se for honey bees (as they can generate it). I do not know if the broad spectrum anti-microbials with which bees are treated (fumagilin, tetracycline) materially affect the gut bacteria -- and this seems understudied. The caution about unintended effects of some of the anti-microbials may have a basis.

One point I want to emphasize: we tend to think of molecules (sucrose,etc) as stable, crystal structures-- dry white granules. In solution, everything is different. Water itself is not the classic "H20" (that is ice). Water are matched but independent ions: H3O+ and OH- floating about trying to bind with each other or any other object with a slight charge. These pairings and uncouplings happen in wild abandon -- equilibrium states of acids and congugate bases driven only by the requirement of convergence toward electro-neutrality. New stable states are solutions with higher likelihood of formation and linkages (such as O double bonds) with lower probability of breakage. Crystallization and precipitation of the sugar rings stops the process. Glucose crystallizes more easily than Fructose, and high glucose nectar harden quickly (any of Mustard family (Canola, Broccoli, Mustard) are an example.


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## barberberryfarm (Feb 16, 2013)

OK. Thanks for that JW. From what you're saying then, it doesn't sound like adding a small amount of ascorbic acid would help that much as the bees already have the natural means to break down the sugar water. Proof of that is I got 4 NUCs this year and they did just fine breaking down the 1:1 sugar water I gave them (until the spring honey flow kicked in) which was also laced with some essential oils (wintergreen, spearmint, lemongrass and tea tree) my mentor suggested I use. Am I ready you correctly?


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## burns375 (Jul 15, 2013)

Tap water is often high in minerals which buffer the pH to the basic side, something like 7-8pH. Water companies not only do this for taste, but to extend the life of pumps and piping by preventing acid corrosion. Perhaps using low mineral, low ppm water will bring the pH closer to range your looking for without adding an acid.


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## JWChesnut (Jul 31, 2013)

Barberberry,
I add a bit of vinegar or a crushed vit C pill to feed. This starts the conversion process. No harm in the addition of the acid donor, and pushes the syrup towards "generic" nectar. The bees will ravenously devour "invert" syrup -- remember the conversion process absorbs H20 from the solution, so the 'brix' post invert goes up. The bees can discriminate relative sweetness very precisely. Human pastry chefs "invert" sugar before making candy because it removes half the water that otherwise would need to be boiled away.

Nectar can vary from 0-100% sucrose. Bee pollinated flowers tend to converge on 20-25-55 in G-F-S mixture. Avocado in my area is 93% Sucrose (and the balance in mostly an indigestible-to-bees 7 Carbon "sugar". Eucalyptus (********) has a large component of indigestible to bees higher sugars. The dangerous aspect of HFCS is the residual starch (ie complex sugars) in the mixture. HFCS is otherwise virtually identical to honey in major component. Some nectar can cause metabolic problems to bees due the prescence of indigestible higher carbon sugars. 

New World native plants (evolved without honeybees) tend to have more frequent non-bee friendly nectar mixes. Hummingbirds prefer all-sucrose nectars. Orchid bees (the typical New World tropic pollinator) have partitioned their feeding niches very narrowly, and some exotic (and semi-toxic to bees) carbo-sugars are an expression of the co-evolution of the specific pollinator and the specific plant.

As I have explained before on this sub-forum, the evolutionary imperative of honey bees is to NOT evolve, but force the plant or the parasite to converge on the bee's requirements rather than engaging in a evolutionary 'arms race' that narrows the generalist's niche. Honey Bees are the preeminent Generalist of the pollinator world. This also informs their relative plasticity to nesting design, brood cycle, etc. Much talk is spent on "optimizing" the nest and yearly cycle for the bee, this is wasted effort, as the BEE DON'T CARE (even more than the famous Honey Badger). Their whole evolutionary strategy is being an organism that can manage to thrive in any situation (nectar, pollen, home, weather) presented.


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## JWChesnut (Jul 31, 2013)

burns375 said:


> Tap water is often high in minerals which buffer the pH to the basic side, something like 7-8pH. Water companies not only do this for taste, but to extend the life of pumps and piping by preventing acid corrosion. Perhaps using low mineral, low ppm water will bring the pH closer to range your looking for without adding an acid.


That's a very good point. Mineralized water will be a H+ sink, and this presents the "invert" of sucrose to the glucose/fructose pair with a real headwind. A syrup mixed with mineralized water will convert much more slowly than a nectar based on neutral to acid phloem sap. Hard water is of course endemic across much of the mid-west and plains states (and some of the opposition to syrup might be local to hard-water localities).

It should be noted that the sugar in plant phloem is typically nearly pure sucrose, and the specialized nectar secreted by the plants into flowers is processed by the plant with enzymes in the nectary cells to produce the attractive mix of Glucose-Fructose-Sucrose for the target pollinator. Plants transport sucrose because it is stable and slow to invert, they don't want acidified fructose messing with their own cells.


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## Jeff Bush (Mar 24, 2013)

JW,

How much Vit. c or vinegar do you add to a gallon of sugar water?


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## JWChesnut (Jul 31, 2013)

Jeff,
The acid is a catalyst -- it initiates a reaction that generates acid end-products.

Water has an enormously variable buffer capacity -- primarily how much of the dissolved positive metal cations are present: Potassium, Calcium or Sodium is present in the source. The balancing negative anions (Chloride, Phosphorus, Sulfur) accompany these. Water exposed to atmosphere will balance to electronegative neutrality by absorbing (and releasing) massive quantities of Carbon (stored as the congugate bicarbonate base: HCO3−) from the sky. It is the absorbtion of CO2 (carbon dioxide gas) yielding carbonic acid in rainwater that starts the metal dissolution process that leads to hard water under limestone soils in first place.

That said, in my own practice: 2 tablespoons of white/apple vinegar per gallon, or 2-1000mg Vit C pills crushed. This is strictly ad hoc (but measured with a pH meter for curiosity).


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## burns375 (Jul 15, 2013)

You know your stuff JW. Chemistry is very interesting....I was on the verge of pursuing Chemical engineering instead went to mechanical. Chemical engineers get payed more, but there were many less jobs available. 

My understanding before reading this was minerals were better for bee health, now im thinking otherwise. I wonder if using distilled or RO-DI water is better than using tap water in syrup mix. I wonder what effect mineral content in tap water has on the bees health. What do you think JW? 


*My tap water quality report*
Alkalinity (as CaCO3) - 73 mg/L
pH - 8.2 Standard Units (SU)
Calcium (as Ca) - 48 mg/L
Magnesium (as Mg) - 7 mg/L
Sodium (as Na) - 33 mg/L
Sulfate - 74 mg/L
Bicarbonate (as CaCO3) - 73 mg/L
Chloride - 38 mg/L
Hardness (as CaCO3) - 144 mg/L
(8.4 grains/gallon)


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## Glen H (Aug 17, 2013)

2000mg equals 1 Teaspoon approx.
I have the powered/granulated Ascorbic acid, that I just started to use.


Glen


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## JWChesnut (Jul 31, 2013)

I wish my water was as nice as your tap water. My ph is 7.5 (we have less alkaline Sulfate at 18) but Cl is 170, and Na is 40, and total hardness is over 200. I live within sight of the ocean. 

This discussion could easily veer into the "Tim Ives- Sugar is deleterious" option. Not sure anyone has demonstrated that sucrose per se damages honeybees (as they are able to metabolize the double sugar quite simply). 

However, there is very good research (May et. al) indicating that specific micro-constituents of nectar have important roles and value. The flavonoid, querceticin, is recently identified as part of immune response flags for bees. Their immune genes are "primed" to express when they encounter the trace flavoring of quercetin in the nectar and natural pollen. (Quercetin is named for the genus of oaks, Quercus, from which it was first isolated).

This raises the question: if nectar (and pollen) micro-constituents are vital, what is the effect of diluting the bee diet with non-flavored syrup and soy-yeast based pollen sub. Not sure anyone has established thresholds for syrup over which bees are harmed by the absence of some missing compound. I believe no one has been able to formulate an artificial royal jelly to raise brood successfully out of the nurse bee's care. The hormones added by live bees are critical; and by extension (speculatively) some natural compound, mineral or flavoring concentrated from nectar and pollen.


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## Tim Ives (May 28, 2013)

JWChesnut said:


> I wish my water was as nice as your tap water. My ph is 7.5 (we have less alkaline Sulfate at 18) but Cl is 170, and Na is 40, and total hardness is over 200. I live within sight of the ocean.
> 
> This discussion could easily veer into the "Tim Ives- Sugar is deleterious" option. Not sure anyone has demonstrated that sucrose per se damages honeybees (as they are able to metabolize the double sugar quite simply).
> 
> ...



http://www.impactaging.com/papers/v4/n7/full/100474.html 

http://www.biomedcentral.com/1471-2164/12/496


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## JWChesnut (Jul 31, 2013)

Tim
Thanks for the references, both of which I had not yet downloaded. I will digest them (and dig through their bibliographies). I am somewhat skeptical of "Resveratol" claims based on the checkered history of the Sirtris drug development.

The papers reinforce the point about vital accessory compounds in pollen (not so much in sugar/nectar) -- though the SIRT1 "caloric restriction" aspect I am just exploring. 

I note the Australian "Fat Bee, Skinny Bee" case studies repeatedly stress the importance of specific species *fresh* pollen in the their sub mixtures. The Australians (because some of the Euc species are fundamentally deficient in Amino Acid balance) have much better real world experience with nutrition than the US. Sunflowers (i.e. the summer forage of the migratory Dakota mega-colonies) are well known for unbalanced Amino Acid profile.

I think you are doing a service by drawing into question the SugarWater+PollenSub approach to colony maintenance that has become endemic due to the Almond gold rush. I think there might be a middle ground where some feeding can strengthen colonies strategically, while some lower threshold of natural sources should not be breached.


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