Treating hard water with Lime, my experience

Not long ago I asked for help on how to reduce my Total Alkalinity as Calcium Carbonate. My Total Alkalinity CaCO3 living in San Antonio, was around 235, which is way too high for many of the light beers that I desire to brew. Two people were quick to help me out and I just wanted to post a follow up on how my water profile before and after turned out.

I followed the instructions in this link Alkalinity reduction with slaked lime - German brewing and more and found it to be really easy to figure out how much lime to use in order to take out the CaCO3. I sent a before and after Wards Lab just to be sure that I wasn't going to change my water to something dangerous and below are the results after following the article step by step using the included calculator.

Before Profile:

Na: 11
Mg: 16
Total Hardness, CaCO3: 183
Sulfate: 11
Cl: 16
HCO3: 220
Total Alkalinity, CaCO3: 235

After Profile:
Na: 11
Mg: 12
Total Hardness, CaCO3: 85
Sulfate: 6
Cl: 17
HCO3: 47
Total Alkalinity, CaCO3: 54


As you can see it worked! Yes, I will have to add salts, but I wanted to show what the water looks like after nothing done to it but the 24 hour Ca(OH)2 treatment. I cant wait to start brewing with this water this weekend. Thank everyone for the quick replies. If you have any questions I will definitely pay it forward by answering as best as I can. Happy brewing!

Wow- thanks for letting us know. Can you give more details, like how you decided to do this? I'll be really waiting to hear how the beer comes out!

I'm buying RO for a portion and treating with lactic or phosphoric acid, and have been considering lime.

The usual limitation is 1 mEq/L (50 ppm as CaCO3). You did well!

Yooper,

You need to start doing this. I always balked at the idea of buying water, especially since it come out of my tap. I've been treating with lime for a number of years after reading AJ Delanges writings on the subject. Even before folks had their water calculators out there. I used trial and error and pH strips to figure out what worked for my water. You have a pH meter which works even better. When I finally got a proper pH meter, my efficiency went up by ~10%

I do my precipitating in my boil pot, let it sit overnight, and then pump it over to my mash tun and HLT. Then I adjust my pH (phosphoric acid - buy the concentrated stuff from Dudadiesel - way cheaper the from a LHBS)

pjj2ba said:

Yooper,

You need to start doing this. I always balked at the idea of buying water, especially since it come out of my tap. I've been treating with lime for a number of years after reading AJ Delanges writings on the subject. Even before folks had their water calculators out there. I used trial and error and pH strips to figure out what worked for my water. You have a pH meter which works even better. When I finally got a proper pH meter, my efficiency went up by ~10%

I do my precipitating in my boil pot, let it sit overnight, and then pump it over to my mash tun and HLT. Then I adjust my pH (phosphoric acid - buy the concentrated stuff from Dudadiesel - way cheaper the from a LHBS)

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I know that AJ has even explained it, and I'm starting to get a grasp on it. But I'm no chemist and find that I don't even really know where to start!

But I will start this when I start brewing again in March, so I have lots of time for research!

so, you do in the BK, which has a diptube, so you can pump it over to the HLT from there and leave the precipitate behind. Then adjust the water, and use it. It sounds simple enough, so that even my little brain can grasp it.

Yooper said:

Wow- thanks for letting us know. Can you give more details, like how you decided to do this? I'll be really waiting to hear how the beer comes out!

I'm buying RO for a portion and treating with lactic or phosphoric acid, and have been considering lime.

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Just like pjj2ba, I did not want to buy any water from the store and at I wanted to know more about the science of brewing so I decided to explore treating my water with lime. The article that I posted has some pictures that give you a step by step of how to do it. I followed it exactly, with the exception that I did not add gypsum to the water before adding lime. I decided to leave that step out since it indicated that it was not necessary. While treating with lime, the pH shot up to ~9.7 and is down to about 8.5 after 24 hours. I've been reading some people talk about how its not the most important thing in the world to have your pH close to 7 before brewing, but I still need another week of research to determine if i need to add an acid to it or if this step is even necessary. Like I said this is my first go around doing this treatment. I'll keep posing updates as I brew my beer with this water and any modifications I make.

BTW Thanks ajdelange!

Drcast128 said:

...I did not add gypsum to the water before adding lime. I decided to leave that step out since it indicated that it was not necessary.

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Extra calcium will precipitate more calcium carbonate and thus remove more alkalinity. For this reason I always tell people that if you are planning to add calcium chloride or calcium sulfate to make up for the calcium dropped in the decarbonation that you should do it before lime treatment, not after. I also advise adding some chalk to the water being treated to serve as nucleation sites for the precipitating CaCO3.

Drcast128 said:

While treating with lime, the pH shot up to ~9.7 and is down to about 8.5 after 24 hours. I've been reading some people talk about how its not the most important thing in the world to have your pH close to 7 before brewing, but I still need another week of research to determine if i need to add an acid to it or if this step is even necessary.

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The pH will continue to drop as the treated water absorbs CO2 from the air. It is very important to get the water off the precipitate ASAP so that the CO2 does not redissolve any of it.

The pH of the water you brew with is not very important. The alkalinity is. The goal of lime treatment is to reduce bicarbonate alkalinity.

Drcast128 said:

BTW Thanks ajdelange!

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Delighted you find the stuff useful.

I brew in a San Antonio and the water is perfect for light beers. I only brew light beer and I put 5.2 at boil and have had no problems. This city is famous for light beers (lone star). The Germans came here for beer.

5.2 would, if it buffered to 5.2, hold the kettle pH higher than you want it to be. But in fact it buffers to a higher pH and is thus definitely detrimental especially when you consider that it adds a lot of sodium. And it can strip calcium.

AJ, you make a good point regarding 5.2. Since it is apparently a phosphate buffer, the potential to complex with calcium could be a possibility. Do you know that that precipitation reaction would or could occur?

ajdelange said:

Extra calcium will precipitate more calcium carbonate and thus remove more alkalinity. For this reason I always tell people that if you are planning to add calcium chloride or calcium sulfate to make up for the calcium dropped in the decarbonation that you should do it before lime treatment, not after. I also advise adding some chalk to the water being treated to serve as nucleation sites for the precipitating CaCO3.



The pH will continue to drop as the treated water absorbs CO2 from the air. It is very important to get the water off the precipitate ASAP so that the CO2 does not redissolve any of it.

The pH of the water you brew with is not very important. The alkalinity is. The goal of lime treatment is to reduce bicarbonate alkalinity.



Delighted you find the stuff useful.

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I went through Kai's writeup very slowly, and I think I get it. I will have to add CaS04 or CaCl2 (as well as the chalk, which I have from winemaking) because my calcium is moderate while my alkalinity is high.

I really appreciate all of your help (and that of Mabrungard as well) in grasping this.

My beer was never not good, and I tend to make darker APAs and IPAs and ambers. My stouts were always by far my best beers and yet I don't love the style that much. My maibocks were always pretty good, while my kolsch and pilsners were a bit harsh.

Once I started diluting with RO water for all by my stouts, and diluting more with the lighter beers, my beer improved greatly.

The funny thing is, now I taste some brewpubs beers and I can "taste" that bad water. Or I can pick out a beer with a yeast in poor that was made. If anything, the better my beers get, the less I enjoy some commercial beers.

Yooper said:

... the better my beers get, the less I enjoy some commercial beers.

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What's the point in home brewing if you can buy better beer?

That's said tongue in cheek, of course. I think the real pleasure comes in being able to brew beer that is better than most you can buy not just in having good beer. I sometimes think this must be the way it is for the extremely wealthy (i.e. the infamous 1%). They take more pleasure in accumulating all that money than in having it. Of course it is very nice to have great beer in the house (and I'm sure it's the same for that first $100 M).

ajdelange said:

Extra calcium will precipitate more calcium carbonate and thus remove more alkalinity. For this reason I always tell people that if you are planning to add calcium chloride or calcium sulfate to make up for the calcium dropped in the decarbonation that you should do it before lime treatment, not after. I also advise adding some chalk to the water being treated to serve as nucleation sites for the precipitating CaCO3.



The pH will continue to drop as the treated water absorbs CO2 from the air. It is very important to get the water off the precipitate ASAP so that the CO2 does not redissolve any of it.

The pH of the water you brew with is not very important. The alkalinity is. The goal of lime treatment is to reduce bicarbonate alkalinity.



Delighted you find the stuff useful.

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Thank you for the reply, ajdelange! I really appreciate your advice and will look into how much to add before lime treatment. I'll try the technique later tonight.

Yooper said:

so, you do in the BK, which has a diptube, so you can pump it over to the HLT from there and leave the precipitate behind. Then adjust the water, and use it. It sounds simple enough, so that even my little brain can grasp it.

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Pretty much. I use a removable filter in my BK so when I treat my water, there is just the bulkhead fitting with short threaded copper adapter sticking into the kettle. The bottom of that is ~1/2 off of the bottom.

When I first started to do this I would transfer the treated water 1 gal at a time to the MT and HLT. Then I had the face palm moment and now just use one of my pumps to move it

Thanks for posting the link along with your numbers, Drcast. Really helpful.

pjj2ba said:

When I first started to do this I would transfer the treated water 1 gal at a time to the MT and HLT. Then I had the face palm moment and now just use one of my pumps to move it

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That's what I was thinking. Treat the water the night before. Then, in the morning, transfer via diptube through the pump to the HLT.

I read Kai's tutorial, but since I don't have an aquarium tester for afterwards as he discusses, it'll have to be a guestimate with some assumptions when I add the CaCl2 and the lime.

I think it's safe to say that if the inorganic phosphate from malt will precipitate calcium from the water that the inorganic phosphate in 5.2 will do the same thing. But that's really what we want as it results in lowered pH (maybe that's how 5.2 is supposed to reach 5.2). We need to be aware of how much calcium has been lost, though, so that we can make it back up if we are doing a beer that needs that.

To go beyond this simple explanation is difficult. I've done some simulations but they are not of practical value - just too complicated.

I've been thinking about this more and more over the last two days, since drcast brought up the subject.

First, I "almost" understand Kai's spreadsheet, and that I have to add a bit of calcium to add temporary hardness. I also should add a bit of chalk to provide nucleation points.

After that, can I still estimate my water's residual alkalinity and the amount of calcium? Or should I send a sample to Ward's Labs? What about bicarb?

Also, is there any downside to this procedure? I've been diluting with RO water, but if this works I can avoid purchasing an RO unit and/or buying RO water. I guess I'm asking is since my Mg (26) is low, my chloride *14) is low, my sulfate is 45, and my Na++ is low, but my HCO3 is high.

Yooper said:

After that, can I still estimate my water's residual alkalinity and the amount of calcium?

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If calcium exceeds bicarbonate (which you can insure by doing supplementation before the treatment) then you can expect that alkalinity will be reduced to about 1 mEq/L, 50 ppm as CaCO3 or 61 mg/L bicarbonate provided that you did everything just right. You can also assume that the calcium will be reduced by the same amount as the bicarbonate. Example: Calcium hardness 250; alkalinity 200 ppm as CaCO3. Reducing the alkalinity to 50 lowers it by 150 ppm and so the calcium hardness will go down by the same amount to 100 ppm (40 mg/L).

Yooper said:

Or should I send a sample to Ward's Labs? What about bicarb?

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If you don't do things just right you will not get to 50 ppm alkalinity and will remove less calcium than desired. Therefore, it is advisable to make a measurement yourself, which is easy enough to do, or send off to a lab. If you do lime treatment a lot its obviously cheaper to do it yourself and you get the answer instantly.

Yooper said:

Also, is there any downside to this procedure? I've been diluting with RO water, but if this works I can avoid purchasing an RO unit and/or buying RO water.

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That depends on whether you have a readily available supply of RO and how hard/alkaline your water is. I've plumbed my brewery for RO and have water that is pretty close to 50 ppm alkalinity so I have to be very precise to get down to 50 and just opening the RO spigot is much, much easier.

The other downsides are that you can't easily get below 50 ppm alkalinity and that calcium is removed. Replacing the lost calcium is almost trivial to the point where I might not even be mentioned aa a down side.

ajdelange said:

If calcium exceeds bicarbonate (which you can insure by doing supplementation before the treatment) then you can expect that alkalinity will be reduced to about 1 mEq/L, 50 ppm as CaCO3 or 61 mg/L bicarbonate provided that you did everything just right. You can also assume that the calcium will be reduced by the same amount as the bicarbonate. Example: Calcium hardness 250; alkalinity 200 ppm as CaCO3. Reducing the alkalinity to 50 lowers it by 150 ppm and so the calcium hardness will go down by the same amount to 100 ppm (40 mg/L).

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So, if my water has 57 ppm and bicarb is 228 ppm, I should add enough calcium chloride to get Ca above 228 ppm? Is that what you are saying? And the Ca will drop by the same amount as the HCO3?

There are ppm and ppm. If your bicarbonate is 228 ppm then the alkalinity is 50*228/61 = 187 ppm as CaCO3. If your calcium hardness is 57 ppm as CaCO3 then you would need to add enough calcium to raise the hardness by (187 - 57). But if your calcium level is 57 ppm as Calcium that amounts to 50*57/20 = 143 ppm as CaCO3 and you only need to increase calcium by 187 - 143. Then, if all goes well with the lime treatment, alkalinity and hardness will both wind up at about 50 ppm as CaCO3 i.e. bicarbonate ion content of 61 mg/L and calcium ion content of 20 mg/L. As you would probably want to supplement the calcium at that level I recommend adding the calcium supplement before the lime addition. This insures that you get the alkalinity down to 50 and perhaps even a little below.

ajdelange said:

There are ppm and ppm. If your bicarbonate is 228 ppm then the alkalinity is 50*228/61 = 187 ppm as CaCO3. If your calcium hardness is 57 ppm as CaCO3 then you would need to add enough calcium to raise the hardness by (187 - 57). But if your calcium level is 57 ppm as Calcium that amounts to 50*57/20 = 143 ppm as CaCO3 and you only need to increase calcium by 187 - 143. Then, if all goes well with the lime treatment, alkalinity and hardness will both wind up at about 50 ppm as CaCO3 i.e. bicarbonate ion content of 61 mg/L and calcium ion content of 20 mg/L. As you would probably want to supplement the calcium at that level I recommend adding the calcium supplement before the lime addition. This insures that you get the alkalinity down to 50 and perhaps even a little below.

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I read that about ten times! My water report shows 207 ppm as "total alkalinity, CaC03" and bicarb (HCO3) as 228, with "total hardness (caC03)" as 251. Ward Labs shows my Ca as 57 ppm. Does that make sense based on what you said about alkalinity?

And of course I was thinking of supplementing Ca by using CaCl2. I assume the Ca would drop, leaving the chloride unaffected.

The lab measures alkalinity which is easy to do and then calculates the carbonate ion concentration from the alkalinity, the water's pH and the end point pH of the alkalinity titration. Assuming that the end point pH was 4.3 and that the alkalinity was 207 the bicarbonate level would be

pH ...... Bicarb
6 ....... 257
7 ........ 252
8 .........249
9 .........227

A lot of people use the approximation bicarb = 61*alkalinity/50 which would give 252 for the bicarb level based on reported alkalinity of 207. If your lab does the math the same way I do (there are popular approximations, labs use different titration end points etc.) a reported bicarbonate level of 228 would imply that your water's pH is around 9. If indeed it is then yes, that makes sense.

Calcium at 57 ppm as the ion implies 50*57/20 = 143 ppm as CaCO3. With total hardness of 251 the magnesium hardness would then be 251 - 143 = 108 ppm as CaCO3 corresponding to 108/14 = 8.9 mg/L.

And yes, the chloride remains untouched in the lime softening process if calcium chloride is used as a calcium source.

Hmm, perhaps you could help me with a quick example for my water, AJ?

Ca 87 (I believe this is as Ca, since it's from a Ward Labs report.)
Mg 9
Sulfate 21
Cl 4
Total Alkalinity 214
Bicarb 261


If my understanding is correct (and if my report is correct...it doesn't balance perfectly though, according to Bru'n Water) that means that theoretically I shouldn't have to add any calcium to my water when doing lime treatment (2.5*87 = ~217)? Obviously I'd want to add calcium for the mash and for yeast health in the ferment.

I tried a 1 liter experimental batch of water using lime amount numbers from Kai's spreadsheet. It got a lot of precipitate, but even after a couple days it still seems like I have what looks like lime suspended in the water (The water is mostly clear, though.). Do you have any idea why this would be?

I've seen lots of Ward Labs reports that don't balance this well.

Assuming the alkalinity is based on titration to 4.3 then a sample pH would be 6.74 would be required to square the alkalinity with the reported bicarbonate.

Calcium at 87 mg/L as the ion corresponds to 217 calcium hardness in ppm as CaCO3. As this is greater than the alkalinity this water is a candidate for lime softening. A trial amount of lime would be 285 mg/L of water to be treated. Either trials with this amount and this amount ± 10% should be carried out and the results analyzed to see which dose is the most effective or one should put about half the water into a container with the lime and gradually add the rest of the water until pH reaches 8 or so.

If there is still something suspended in the water it is probably excess lime - IOW you added too much. But I would expect even that to settle after a couple of days.

ajdelange said:

If there is still something suspended in the water it is probably excess lime - IOW you added too much. But I would expect even that to settle after a couple of days.

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I was guessing that too, but I thought I'd ask. It tasted kind of alkaline...at least from my limited experience with alkaline liquids. Anyways, thanks for the info!

Update: I tasted it again. It actually tasted pretty normal this time. The aquarium test strips I have for alkalinity (I'll have to get better strips if I continue to do this.) seem to indicate that the alkalinity ended up between 0 and 80. I think some of the stuff that appeared to still be in suspension was really just stuck to the walls of the pyrex container.

revolutioned said:

I brew in a San Antonio and the water is perfect for light beers.

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It's actually the opposite. The RA is San Antonio is over 80, which puts you in the "dark amber approaching stout/porter" range. Brewers in the area either dilute with RO water or build from 100% RO water.

FWIW, Austin water is better (RA = 40) because the city treats the water with lime.

Apologies for restarting this portion of the thread.

ajdelange said:

The lab measures alkalinity which is easy to do and then calculates the carbonate ion concentration from the alkalinity, the water's pH and the end point pH of the alkalinity titration. Assuming that the end point pH was 4.3 and that the alkalinity was 207 the bicarbonate level would be

pH ...... Bicarb
6 ....... 257
7 ........ 252
8 .........249
9 .........227

A lot of people use the approximation bicarb = 61*alkalinity/50 which would give 252 for the bicarb level based on reported alkalinity of 207. If your lab does the math the same way I do (there are popular approximations, labs use different titration end points etc.) a reported bicarbonate level of 228 would imply that your water's pH is around 9. If indeed it is then yes, that makes sense.

Calcium at 57 ppm as the ion implies 50*57/20 = 143 ppm as CaCO3. With total hardness of 251 the magnesium hardness would then be 251 - 143 = 108 ppm as CaCO3 corresponding to 108/14 = 8.9 mg/L.

And yes, the chloride remains untouched in the lime softening process if calcium chloride is used as a calcium source.

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AJ I have a question if you don't mind. Where did you get these equations from? 50*57/20 = 143 and bicarb = 61*alkalinity/50 I'm trying to follow the posts that were put up in the past few days and maybe I missed the post where these numbers and equations are coming from, if that's the case, very sorry.

I was wondering. Since my post lime treatment turned out to be pretty decent, can I simply add salts post lime treatment? What would be the drawback to doing so? If I added salts before treatment with lime would I have to add extra salts due to some Ca precipitating out of solution? Thanks!

If you put 100 mg of calcium carbonate into 1 L of water and dissolve it with enough CO2 to get the pH to 8.3 the following reaction takes place

CaCO3 + H2O + CO2 --> Ca++ + 2HCO3-

100 mg is 100 millimole so the result of this reaction is 1 mmol/L Ca++ and 2 mmol/L HCO3-. When alkalinity is measured a strong acid is added to the sample which converts the bicarbonate to CO2 which then escapes the solution

2H+ + 2HCO3 ---> 2H2O + 2CO2

Thus 100 mg ~ 1 mmol of calcium carbonate required 2 mmol of acid (H+) which, as protons are singly charged, is 2 milliequivalents. Going back to the 1 mmol of Ca++ per liter, that is doubly charged and so 1 mmol/L Ca++ ~ 2 mEq/L. Thus each milliequivalent of calcium and each milliequivalent of bicarbonate corresponds to 50 mg/L calcium carbonate dissolved with CO2. Nature dissolves CaCO3 with CO2 so it seems natural to express the alkalinity in terms of the amount of limestone nature would have dissolved with CO2 to produce that level of alkalinity. While that may be handy what we are really after is equivalence. Fifty ppm as CaCO3 corresponds to 1 mEq/L and that's the basis of the formulas. WRT calcium: its atomic weight is 40 i.e. 40 mg of it is one mmol which, since it is doubly charged is 2 mEq. This the equivalent weight is 20 mg. Twenty mg of calcium is 1 mEq. Thus if I have 57 mg/L Ca++ I have 57/20 mEq/L. As 1 mEq/L corresponds to 50 ppm as CaCO3 57 mg/L Ca++ ~ 50*57/20 ppm as CaCO3. The reasoing is exactly the same for the bicarbonate. We divide the alkalinity in ppm as CaCO3 to obtain the number of mEq and then multiply by the equivalent weight of bicarbonate ion which, as it is singly charged, is the same as its molecular weight i.e. 61.

Yes, you can add salts post treatment but as additional calcium helps in the precipitation of calcium carbonate I suggest adding calcium chloride and calcium sulfate before the lime treatment. And yes, you must account for the calcium dropped by lime softening in computing the total calcium in the treated water.

Thanks for posting this Drcast. I have been purchasing water for lighter beers (and figuring even the crappy SA water can't overpower darker beers). I really would like to learn more about water chemistry to cut down on costs and use the water straight out of the tap.

What part of the city are you in, and do you get your water through SAWS or BexarMet? I'm not sure how different their water makeups are, but it would be beneficial to know which water company makeup the numbers of your first post reflect.

I have my own success story to mention! I successfully produced just over 9 gallons of ~3dH water (The color seemed like it may have changed at 2dH (drops in the kit), but I wanted to air on the side of slightly higher alkalinity.). I'll be interested to see how my beer turns out! It's certainly cheaper than bottled water in these parts (We don't have RO machines in these parts). For a light beer I often have to buy ~7.5 gallons of water, which is around $8-9.

D_Ranged_Eskimo said:

Thanks for posting this Drcast. I have been purchasing water for lighter beers (and figuring even the crappy SA water can't overpower darker beers). I really would like to learn more about water chemistry to cut down on costs and use the water straight out of the tap.

What part of the city are you in, and do you get your water through SAWS or BexarMet? I'm not sure how different their water makeups are, but it would be beneficial to know which water company makeup the numbers of your first post reflect.

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No problem, I hope it helps! I live right across the street from the medical center and I believe my water comes from SAWS, based on the service area charts I found online. I brewed two batches of beer this weekend with my lime treatment and CaCl additions. I tried the water before brewing and the difference between the two is night and day! I'm going to lager one and do a pale ale for the other one so I'll let you know in a few weeks how it all turns out (fingers crossed). I would encourage you to at least try the lime treatment. So far its really not as hard as I thought it would be. If you have any questions let me know.