Kalk & Vinager

[MikeS]

Hi all

Having an interesting discussion with Clkeep in the Reefs Forum about calcium and such....a good question came up but I think it's buried in that thread deep enough that not too many people might see it, so I thought I'd post it here....

Have any of you who dose Kalk experimented with adding vinager to the solution to increase the solubility of the Ca in the mix? If so....what is your mix ratio? Also have you experienced any negative effects by adding vinager to your tank?

MikeJS

[Charles Poole]

I found some articles by Craig Bingman. At the moment it would seem that Reefs.org and animalnetwork are having some database problems. At present, it would seem that none of the links I have tried, even the ones provided by them do not work.

Here is an archived thread over at reefs.org that did work, quite lengthy, but very informative on the issue of vinegar (Acetic Acid) and Limewater additions.
http://www.reefs.org/cgi-bin/ultimatebb.cgi?ubb=get_topic&f=26&t=000096

Here is the link to Craigs article, give it a try and see what happens.
http://www.animalnetwork.com/fish/library/articleview2.asp?Section=&RecordNo=181

If you are able to access Craigs Article, please let me know... :)

Also, in the interest of science, could you add 1 more tsp. of kalk to your normal 2 tsp. then test and see if there is a corresponding change in Ca++ levels. From your earlier results, this should test around 570 ppm Ca++. Which is what Kent's Kalwasser tested for me.

[Charles Poole]

What I can tell you is that the vinegar is supposed to be added to the kalkwasser before it is mixed with water. Something to do with saturation levels of CaCO3 ( Calcium Carbonate ). It provides a proper amount of available CO2 rapid enough to form this ion, and helps to allow the water to become saturated at seemingly higher levels.

My description may be slightly generalized or partially inaccurate, so please don't take it for face value. My testing coupled with Mikes will help shed a little more light onto the understanding of this chemical cocktail.... :)

[MikeS]

well, I read the thread at reefs.org.....lots of good info....the animal network link didn't work....

Here's what I got out of it ( I skimmed through the tread pretty quicly, mind you) ...the use of vinager as a premix to a kalk solution has four main advantages.... 1. it allows more complete saturation of Ca in the solution. 2. The saturation occurs much more quickly. 3. it helps counter the negative effects of CO2 on kalkwasser, reducing the amount of bicarbonate to carbonate transformation in the tank once dripped. 4. it produces free carbon which helps the bacteria bed.

one person in the tread reported clumping or cementing of his substrate while using vinager, but he was using a very small amount so this could be due to other things. The person giving most of the information claims he has been doing it for years with no negative effects on his tank.

If all of the above are true, it seems this is something definately worth experimenting with. I think I'll mix a batch with vinager and test it for Ca, pH, and alkalinity to see what I get.

MikeJS

[Charles Poole]

Mike,

What amount of vinegar should we use at the start?

I am thinking around 5 - 10 ml per 2 tsp. of Kalkwasser. What are your thoughts?

I used 2 tsp. of Kent Marine's Kalkwasser for our previous testing, so I will stick with that amount in the interest of noticing changes. Let's try and keep the controls as similar as possible... :)

[MikeS]

that's good...I'm going to try the vinager.

I tested a batch of kalk (Mrs. Wages) without vinager....mixed at 3tsp/1gal. Heres what I got

580ppm calcium
21 meq/l carbonate alkalinity
60 deg carbonate hardness on a different test kit
pH was off the scale of my test kit, the highest one I have only tests to 9.0 pH


I'll mix up a batch of kalk tomorrow...2tsp/1gal, and 20 ml vinager.
(1/2 tsp/quart-5ml vinager)

MikeJS

[Charles Poole]

Mike,

Your results do show that we are on the same page. With the addition of 1 more tsp. you got the results we expected. Although the Alkalinity is a bit lower, this is not a really significant amount. Converting dKh to meq/L shows approx. 21.7 meq/L. Which is pretty close to what we expected to get.

In short, Kents Kalkwasser is approx. 33% more concentrated that Mrs. Wages Pickling Lime. On a price comparison, it would seem that Mrs. Wages wins in the end. :)

The conversion from dKh to meq/L and vise versa is:
dKh / 2.8 = meq/L
meq/L x 2.8 = dKh

After we get this figured out a bit more, I am going to do some Magnesium testing and Calculations. As a lower than NSW level of Magnesium can interupt the amount of Calcium and Alkalinity that can remain in solution without precipitating.

Anyone got a copy of Spottes "Captive Seawater Fishes" or Millero's "Chemical Oceanography"? :)

[MikeS]

how long after mixing the kalk/vinager solution should we wait before testing?

Mike

[Charles Poole]

From what I got out of the articles that where available is to mix the kalk into a paste with the vinegar then add water. I shake the mixture of kalk once every hour for 3 hours, then let it settle for atleast 2 hours.

When I first mix the kalk, I shake it up vigorously for a minute or so. My test results from the 5 hour mark to the 24 hour mark haven't changed, so I am assuming this is sufficient enough.

On another note, what is your Magnesium level? If your magnesium level is to low in your aquarium, you may find odd or seemingly inaccurate levels of calcium and/or alkalinity. It is something to look into as an explanation to your strange readings when dosing Turbo Calcium.

Also, with additions of either calcium or alkalinity being done seperately, you run the risk of precipitating one or the other out of solution. That may be why dosing kalkwasser has work the best for you so far, as kalk adds both at the same time... :)

[MikeS]

I mixed the vinager/kalk at this ratio:

1 tsp Mrs Wages
10 ml of 5% acid white vinager
2 quarts water.

My dosing jug is a 2 quart jug, so I mixed at the 2tsp/20ml/1gal ratio, since this is where I'll start my dosing at initally. I notice that there is very little residue at the bottom of the jug compared to before....

My magnesium level in my tank is currently at 1000 ppm. I checked the kit against the calibration sample, it checked out, so I'm confident in this number. A bit on the low side, but I always expect that since I use limewater. I know most other reefers who dose limewater have lower magnesium levels, but they don't seem to panic unless the level drops below 700ppm.

My reef is about 3 1/2 years old now, and it has always seemed to suffer from a low alk/high pH/lower calcium syndrome. I'm really hoping that the use of this vinager-kalk mix will help this situation out. I asked Randy over at Reef Central a few breif questions about pH, he seems to think it will definately help my tank. I'm also switching to Baking Soda instead of the ProBuffer, from what I've read this should further help my problem.

I'll post some test results on the kalk later tonight....

Mike

[Charles Poole]

At levels below 1100 ppm, it is nearly impossible to maintain a good ionic balance with respects to Calcium and alk.

At around 1100 ppm you will keep dosing and dosing, but never reach the mark you are shooting for. This low level creates a situation that allows CaCO3 to precipitate at much faster rates than normal.

Mike, that is a dangerous practice, and I suggest raising the level to 1250 ppm or slightly higher. I say this with experience, as I lost half my tank due to reduced Mg levels. It is need by more than the buffer system. Most organisms have a level of Mg in them in direct proportion to NSW, so low levels equals major problems. Hence an inability to raise alk or Ca to a predetermined tested value.

[MikeS]

I have some magnesium...I've started to bring that level up.....

Here are the results on the kalk I mixed about 6 hours ago (1tsp kalk/10ml vinager/2 quarts h2o)

calcium 400ppm (increase of 20ppm from earlier test on kalk w/o vinager)
total alkalinity 17 meq/L
pH still greater than 9.0

all I have for pH test kits are a couple of those cheesy "compare the color" ones (my pH meter is DOA)....and the highest either of them reads is 9.0. Is there any way to dilute the sample with a neutral pH solution like distilled water in equal parts and come up with a reading? Just curious if you have any ideas....



Mike

[Charles Poole]

I am not sure how to dilute this mixture to lower the pH with any accuracy.

I will look into it and see what I can come up with. :)

[MikeS]

OK here's an update

I've been dosing the vinager/kalk mix (10ml vinager/1tsp kalk/2 qt. water) 1 batch nightly dripped, for a week now. To try and help my high pH/low Alkalinity/low magnesium problem I have also been adding the following things to the tank:

2 tsp Arm& Hammer baking soda- 2 doses of 1 tsp/1 pint water daily
5 tsp seachem reef magnesium in 1 quart water (this should give me a roughly 15ppm increase in magnesium daily)

After 1 week of this, my tank water tests as following:

Magnesium= 1190ppm
Total Alkalinity= 3.4 meq/L
pH holding around 8.4

Calcium= 250ppm ! :shock:

why is the calcium so low? any ideas on what is going on?

Mike

[MikeS]

Ok read Randy's article on Calcium & Alkalinity AGAIN :D it seems maybe I overdid it with the buffer....he recommends using Calcium Chloride to get the calcium levels back to normal, no buffer, and no limewater....once I get these back to normal, should I be able to start dosing limewater again?

Mike

[Charles Poole]

Don't ya hate it when you answer your own questions.

Just be careful with the CaCl2, as it can have the same affect on Alk, as the Alk has on calcium.

Let me know how it goes. Sorry I haven't posted my Kalk and Vinegar results yet, but I ran out of Calcium test kits, and I have to wait for our next shipment to arrive this Thursday.

I will get back in the groove on Friday I promise... :)

[MikeS]

Yeah, I think this will have to be a long-term kind of post... :D

I'm only going to use the turbo calcium long enough to get my ca levels back up to 380-400ppm, (at around 30ppm a day I think) then I'm going to switch back to the kalk and vinager, but keep a closer eye on alk vs calcium. When using the calcium chloride, if my alkalinity drops, should I add the baking soda?

Mike

[Condiman]

This dose sound promising excellent work chuck

[Charles Poole]

As long as you don't over shoot your goal by to far, you can let it drop back down on its own. If you go to far, then Alk may start to drop.

Easiest way IMHO would be to do a 25 - 35% water change, the make adjustments. This eliminates any other possible factors, and brings the balance closer to where you want to be. Safely.

[MikeS]

yes, planning a 25% water change for this weekend. (been a month, so it's due....)

Mike

[Charles Poole]

OK, test kits are in, and I am preparing to become a "mad" scientist again... :lol:

I will post my results later on... :)

[MikeS]

OK...here is my tank water today (I haven't done the water change yet)

Magnesium 1350 ppm
Total Alkalinity 2.0 meq/l
pH 8.3
Calcium 300ppm

now that I have the magnesium levels where they need to be, I can hopefully get to the 400ppm calcium mark a little quicker using the calcium chloride. I'm going to try to slowly adjust the alkalinity up to 2.5-3.0 meq/L using small amounts of baking soda every day until I hit it. I'm going to try hard not to throw it out of balance again...Once I hit my target levels, I'm going to go back to the kalk & vinager and see what happens.

Mike

[MikeS]

well....still at it....

my calcium is holding @ 420 ppm
Alk goes up and down but rarely drops below 2.5 meq/L, I still need to use baking soda every other day or so, but only 1/2 tsp.
pH usually around 8.3

I have noticed that the vinager boosted Kalk does not drive down my magnesium levels as bad as it did before I started using vinager....any guesses on why this is?

Mike

[gman0526]

Is there an update on this thread guys?

[FishinInTheDark]

Yes, Mike started floating cucumbers in his tank. The salt, vinegar and pickling lime have done their work. He is now bottling these new pickles, and the time his new business requires keeps him from testing his water and updating us on his progress. . .

:D Conni

[MikeS]

:lol:

Yep, she's got it.... :D

Still doing the vinager boosted kalk....I'm up to 40 ml/ 2.5 tsp Mrs Wages/ per gallon of makeup water...I'm happy with the results so far.

My calcium levels drop more slowly than they did with regular kalk, my alkalinity stays higher, and my pH is a nice stable 8.3.

No negative side effects so far....

After a few more months of doing this, I'm going to write a short article on it.

Mike

[cich1]

mike is the baking soda dosed separately from the kalk/vinegar mix or can it be added at the same time? also do you mix the baking soda with top off water or add it directly to your tank?

[gman0526]

Cool Mike, sounds good!!!

BTW Conni LMAO

[MikeS]

I mix the baking soda alone in RO/DI water and use seperately as needed to adjust alkalinity. my pH stays a pretty constant 8.3


Mike

[gman0526]

So what's the story Mike? It's time for the monthly update... :D

[MikeS]

still going good.... :D

Mike

Good article on the issue http://www.reefscapes.net/articles/breefcase/kalkwasser.html

Here's the Animal Network article
http://web.archive.org/web/20030608113249re_/www.animalnetwork.com/fish/library/articleview2.asp?Section=&RecordNo=181

I recommend using vinegar (white not yellow) with Kalk.
First, it will get more Calcium ions (Ca++) into the solution because you are dissolving the Ca(OH)2 in an acid instead of water, and forming Calcium Acetate, which exists as a dissociated equilibrium of free Calcium ions and Acetate ions.

Second, the Acetic Acid (Vinegar) provides an equivalent of all the CO2 you need to avoid precipitating the newly-added Calcium ions as useless white Calcium Carbonate powder.

Third, after all the cool Calcium ion chemistry is over, the leftover Acetate ions from the broken-down Vinegar leaves you with free organic Carbon in the water that feeds the bacteria in your tank so that it converts more poisonous Nitrates to NO2 gas (a very good thing).

[MikeS]

mantisfreak....do you use vinager boosted kalk? If so, would you share your mix ratio (including brands) and any interesting info you might have on it?

Mike

My Kalkwasser is from Two Little Fishies which is Julian Sprungs company. He sells a number of products that I don't like at all but I have had good experience with his Kalk.

I'm an accountant so I stopped using vinegar around January....too much coralline. By the time I got home I was exhausted and was NOT in the mood to scrape my glass. Even though I stopped using vinegar, there was enough there to almost cover my front glass.

I don't believe in overloading Calcium....I believe in balanced chemistry. If your tank isn't using all of the Calcium from regular Kalk, there's no reason to add vinegar.

I wish I could give you a recipe. I own a Pinpoint pH monitor and at this point, I can tell if I added too much vinegar or too little based on that. (Other than my skimmer, the monitor was the best purchase I have ever made on my tank...you can deduce Calcium and Alk very easily based on it without titration). Basically, I mix my Kalk the way I make my chili...a little of this, a little of that. This is not good practice and I DO NOT WANT OTHERS TO FOLLOW MY LEAD.

I literally don't measure at all....I just eyeball it. I don't know how to describe my "eyeball" measurements.

Here's another good article http://web.archive.org/web/20030418110415re_/www.animalnetwork.com/fish2/aqfm/1999/oct/bio/default.asp

[MikeS]

I'm up to 50 ml white 5% vinager/3 tsp Mrs Wages/per one gal RO/DI...my alkalinity levels are better than they were before I started, as is my pH, but I still have problems keeping alkalinity where I like it...I'm wondering if that has something to do with the lower purity of Mrs. Wages compared to commercial kalk powders...but at less than $2/Lb, I'll stick with the Mrs Wages...

Mike

[Sugar Magnolia]

Has anyone tested this vinegar addition with any other brand of kalk powder. I'm using a kent kalwasser and wondered if the results would be the same. My alk is always stable at around 9 dKH but my CA is always on the low end ~380. I've been adding ESV's Calcium Chloride pellets a couple times a week disolved in RO/DI water to try and maintain a decent level, but I seem to only get up to around 420 then it drops again. So far it hasn't supressed my alk like I was told it would. I guess the two clams and the giant frogspawn in my 30 are sucking up major CA.

I suppose I could (GASP!) mix some up myself and test it, but since I am severely deficient in the testing area of this hobby it'll take some serious motivation.

[MikeS]

I have read several articles and also threads in other forums, I have seen a variety of different kalk powders used in these mixtures. This method should work just fine with any of the commercially available kalk powders, as well as pickling lime. Your results will probably be better with a more pure form of kalk, like most of the commercially available ones, compared to pickling lime.

If you choose to experiment with this, go into it slowly...I started with the normal amount of pickling lime I normally used and started slowly adding increasing amounts of vinager to the mix. Be sure to carefully monitor pH, alk, and calcium levels in your tank as you do this. Also keep an eye on the general health of the livestock in the tank, in case they show any adverse reactions...

Mike

[Sugar Magnolia]

Thanks Mike. I use about 2 tsp of the Kent kalk powder to a gallon of RO/DI...how much 5% white vinegar would you advise I start with?

[MikeS]

I'd start with about 5 ml...and work your way up 5 ml a week increase....

Mike

[Sugar Magnolia]

I tested my water today before beginning this vinegar trial. I was pretty surprised at my Ca reading, but then remembered that I had dosed some ESV calcium carbonate two days ago. Anyway readings were:

pH 8.2
Ca 460
alk 3.31 meq/L
dKh 9.3
Mg 1170

Low Mg, so I just dosed some Seachem magnesium that I had purchased a while back and I'll retest it tomorrow to see if it went up at all.

I had mixed up my gallon of kalk top off water last night and checked your recommendation earlier today to dose 5 ml Mike, and did just that to my premixed kalk water, but then just now went back and read through the thread which suggests mixing the kalk powder and vinegar to form a paste, then adding it to the RO/DI. Oops. Oh well.

[MikeS]

I don't think the order the ingredients are added makes a real big difference, but most of the info I've read on it from people who use it recommend mixing the vinager and kalk first, then adding the water...

Mike

Yes, you want to dissolve the powder in the full strength vinegar. Not diluted vinegar.