Let's Talk "chlorine" - What Is It Really?

NeonBlueLeon

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Hello folks,
 
Chemist here.  I have had experience with almost all chlorine compounds in the lab, and as a matter of fact, in swimming pools (formerly CPO certified).  My exposure to all kinds of chlorine compounds range from minor explosions in the lab, wooziness from inhalation, burned skin, and ruined clothing.
I thought a brief "course" of relevant chlorine compounds would help the community better understand what these chemicals actually are.
Note that some of these chemicals are in fact dangerous, but in terms of what comes out of the faucet, it is on a small enough scale that little harm can befall onto humans.  So don't go buying gas masks and heavy duty gloves to put on when turning on the tap.
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  However, there are enough of these chemicals to harm fishies, which is why we as aquarists have taken interest in these chlorine compounds.
 
There are four chlorine compounds I want to discuss:
1) Chlorine: Cl2  - When one says "chlorine," the technical meaning is a chlorine molecule.  That means two Chlorine atoms bonded together.  This stuff is a green gas.  It was used in WW1 in chemical trench warfare.  When aquarists say "chlorine," they do not mean chlorine gas.  More on that later.  Chlorine cannot be present in water (would just evaporate out and poison you instead).  Needless to say, this stuff is very toxic to breath in, but in terms of aquariums, don't worry about it.  Side note: if you see a greenish gas that seems heavier than air coming towards you, run the other way.  Just kidding, but not really.
 
 
2) Chloride: Cl-- Chloride is the ionic form of chlorine.  For any chemistry buffs, it's atomic chlorine with an extra valence electron.  This is what table salt is when you dissolve it in water.  Similarly, this is also in aquarium salt and, of course, ocean water.  Aquarium salt and ocean water have traces other salt compounds in it that are not harmful to fishies.  Anyone who treated Ich with salt obviously knows chloride is not harmful to your fish.  Even scaled freshwater fish can deal with relatively high levels of salt (aka chlorides) in the water for a temporary period of time.  There is no need to remove chlorides from your tap water, and tap water conditioners do not remove it.  Note: the effect of chlorides on some invertebrates and scaleless fish is very different.
 
 
3) Hypochlorite: ClO-- Now we're talking dangerous for fishies.  Hypochlorite is what aquarists and tap water conditioner bottles refer to as "chlorine."  This is the stuff found in household bleach, also labeled Sodium Hypochlorite.  It is also used in swimming pools, and has the recognizable "chlorine" or bleach smell.  In high concentrations, this will eat up virtually anything.  Luckily, they don't sell this stuff in high concetrations to the public.  The good news is, small amounts of hypochlorite is easily washed away with plenty of water. 
 
However, there are trace amounts of hypochlorite used to keep tap water clear of bacteria and parasites.  The main concern of the water department is E. coli strains.  Unfortunately, that means after you've bleached your new or quarantine tank and decorations, rinsing with tap water doesn't make it free of hypochlorite.  Thankfully, tap water conditioners contain polyvinylpyrrolidone.  This is very cool stuff.  It is a polymer, much like plastic, but dissolves in water.  And it locks up hypochlorites!  I mean it literally locks it up into the polymer so it cannot harm your fishies.  All tap water conditioners have polyvinylpyrrolidone in it to detoxify hypochlorite.
 
 
4) Chloramines: NH2Cl/NHCl2/NCl3 - Oh boy is this stuff really bad for your fishies.  With enough of it, it will knock out your fishies' respiratory systems.  Do not panic yet, because there is good news.  Although some water departments still use chloramines for treatment, most use only hypochlorite.  Hypochlorite was found to be about three times as effective, and much less toxic to humans.  More good news: chloramines are easily neutralized by sodium thiosulfate, which is found in virtually all tap water conditioners.  Prime has the highest concentration of sodium thiosulfate, which is why it smells of sulfur, but other conditioners will work perfectly.  Another thing to note is some people may say that carbon will remove chloramines.  However, only medical grade carbon can remove chloramines, and not even remotely effectively as sodium thiosulfate.  Medical grade carbon is much too expensive and is inaccessible to the average aquarist.
 
The dangers of chloramines appear when you have ammonia in your aquarium.  Ammonia reacts with any and all hypochlorites in the water to form the very dangerous chloramines.  So take home lesson about chloramines?  Hypochlorites are bad enough, but hypochlorites with ammonia is double-- no quadruple jeopardy!
 
 
 
Some other chemistry notes related to aquariums:
 
-Some tap water conditioners have EDTA in them.  EDTA "locks away" dissolved metals from the water such as iron, copper, and magnesium.  The ability of EDTA to lock away chloramines is slow and takes days.  EDTA will not affect iron supplements for plants (iron fertilizers are already chelated).  Point is, EDTA is not an effective hypochlorite or chloramine remover.  I do not know about the toxicity of EDTA in fishies, but it is not a good thing for humans to be over-exposed to.  In the old days, EDTA was given to people to drink who had metal poisoning.  I personally shy away from conditioners that have EDTA in them.
 
-Ammonia (NH3) is actually a misnomer.  Any ammonia in water would just evaporate out.  The ammonia excreted by fish is better known as ammonium (NH4+), which in water has the form NH4OH. In actuality, the relationship of ammonia and water is very complicated and is not easily explained without a chemistry background.  This was just for a bit of knowledge for aquarium trivia.
 
Excellent information. We do often use common terms like ammonia in the hobby as a way to simplify things.
 
I found, "The dangers of chloramines appear when you have ammonia in your aquarium.  Ammonia reacts with any and all hypochlorites in the water to form the very dangerous chloramines.  So take home lesson about chloramines?  Hypochlorites are bad enough, but hypochlorites with ammonia is double-- no quadruple jeopardy!" to be of particular interest. Can you expound on how this might occur in the average aquarium and how it can be prevented?
 
Thank you for this interesting article!

Like tcamos, that paragraph about chloramines caught my eye. I had thought that chloramine was an unstable compound and will not form spontaneously, indeed water suppliers have to work hard to get it into the water. Am I wrong?
 
Good stuff NeonblueLeon I normally hate anything remotely to do with chemistry, but I actually followed what you were saying so thanks for that! There is hope for me yet!
Have never suggested this before and don't know if it's appropriate now, but I think this could and should be pinned for all to see.
 
daizeUK said:
Thank you for this interesting article!
Like tcamos, that paragraph about chloramines caught my eye. I had thought that chloramine was an unstable compound and will not form spontaneously, indeed water suppliers have to work hard to get it into the water. Am I wrong?
You're right, chloramines are dangerously unstable in high concentrations. In low concentrations, such as in tap water, it is quite stable and acts as a disinfectant. Since the chloramine section has sparked interest, I will be expanding on the section in just a bit. :) I ran to the department library and did some searching on chloramines and found some new stuff.

Mamashack said:
Good stuff NeonblueLeon I normally hate anything remotely to do with chemistry, but I actually followed what you were saying so thanks for that! There is hope for me yet!
Have never suggested this before and don't know if it's appropriate now, but I think this could and should be pinned for all to see.
Glad you were able to follow! :) I have hopes one day to be a chemistry teacher at a university. In my opinion, more people could be interested in chemistry if only it were more approachable. I wish to be the teacher that makes the subject relatable and understandable to students.
 
NeonBlueLeon:
 
Glad you were able to follow!
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I have hopes one day to be a chemistry teacher at a university. In my opinion, more people could be interested in chemistry if only it were more approachable. I wish to be the teacher that makes the subject relatable and understandable to students.        
Well if you can get me to understand anything remotely to do with chemistry, I'd say you're well on the way to achieveing that NBL. Usually I can feel the shutters coming down, but I could follow your post and it was such a relief so thanks again!
 
Here's some more info about chloramines since they seem to be of interest!
 
First off, I have looked into recent developments in water treatment.  I was under the impression that water treatment facilities have been shying away from using chloramines additives as a disinfectant.  This is actually untrue.  Recent EPA policies have been causing some water treatment facilities to switch to chloramines from hypochlorite for a number of reasons.
- The chemical products of hypochlorites disinfecting contaminations in water (i.e. bacteria and waste) are harmful and “unpredictable.”  Basically, when hypochlorite attacks unwanted materials in drinking water, the resulting chemical can be also dangerous, and there are many different products that can form.  The products formed from chloramines are supposedly less harmful, and can be predicted more easily.  More on this below.
- The EPA has new policies on the maximum amount of hypochlorite that can be in tap water.  This has caused a hassle for water treatment facilities, so some of them have been adopting chloramines as a disinfectant for tap water.
 
That being said, chloramines are now of reasonable interest to us aquarists.  So let’s delve deeper into what chloramines are.
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Chloramines are nasty to fishies in exactly the same way carbon monoxide is dangerous to humans.  Chloramine binds to the blood in fish much more strongly than oxygen does.  With enough chloramines binding to a fish’s blood, the fish will eventually suffocate and die.  This is the same poisoning process that occurs when humans are exposed to carbon monoxide.  Carbon monoxide binds thousands of times more strongly to hemoglobin (iron in our blood) than oxygen.  Enough exposure to carbon monoxide will silently suffocate us humans to the point where vital organs fail.
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Now, the “nightmare” scenario I depicted above, where hypochlorites and ammonia are present in a tank, is hopefully uncommon.  The reason why I brought that up is because hypochlorite readily reacts with any ammonia in the tank to form chloramines.  If this is the case, the tank would be swarming with fishy poisons.  This stresses the importance of treating tap water and properly cycling a tank.
 
The last point I want to add about chloramines is about the chemical product that forms when chloramines disinfect a contamination.  The common product is—dun dun dun—ammonia!  Say you’ve added tap water conditioner to your source of tap water, and it contains chloramines (now neutralized).  Also, say you have an algae colony growing somewhere in your pipes.  The algae presumably has been destroyed by the chloramines, but now you’ve got trace amounts of ammonia in your water!  Lucky for you, your tank is cycled.
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These trace amounts of ammonia in the water are apparently not of concern to the EPA.  I have never quantitatively determined how much ammonia could  be in tap water, so I don’t want to say whether or not this is safe for humans.  In terms of our beloved fishies though, the ammonia would be consumed by our bacteria.  If however you tank is uncycled, well you have a more important ammonia source to worry about than the trace amounts in your tap water!
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That's what I've got for now.  If there's any questions, confusion, or even further curiosity, I am at your service!
 
So under those circumstances, even in a cycled tank, we could expect a nitrate spike as the bacteria that consume ammonia have more food, producing nitrite, etc. etc.
 
Yes plenty of water suppliers use chloramine (mine does).  What I don't think has been mentionned yet is that neutralizing it with a water conditioner actually does so by converting it to ammonia anyway.  This is why I use Seachem Prime because it locks up the resulting ammonia for a while giving the filter a chance to deal with the influx during a water change.  Prime is therefore a really good choice for anyone with chloramines in their supply.
 
Also some of the chloramine will naturally breakdown into ammonia while in the water supply.  This leads to colonisation by nitrifying bacteria within the water supply and you end up with nitrates coming out in your tap water.  I assume this is one reason why my tap water comes out at 50ppm nitrates!
 
tcamos said:
So under those circumstances, even in a cycled tank, we could expect a nitrate spike as the bacteria that consume ammonia have more food, producing nitrite, etc. etc.
Depending on how much ammonia results from chloramines, you may or may not get a spike in nitrates.  Unless there are substantial amounts of contaminants in the water source, the amount of ammonia produced by fish will far outweigh the amount of ammonia already present in tap water.  In the end, nitrates are nitrates and there's no real way of saying exactly where they came from.
 
daizeUK said:
Yes plenty of water suppliers use chloramine (mine does).  What I don't think has been mentionned yet is that neutralizing it with a water conditioner actually does so by converting it to ammonia anyway.  This is why I use Seachem Prime because it locks up the resulting ammonia for a while giving the filter a chance to deal with the influx during a water change.  Prime is therefore a really good choice for anyone with chloramines in their supply.
 
Also some of the chloramine will naturally breakdown into ammonia while in the water supply.  This leads to colonisation by nitrifying bacteria within the water supply and you end up with nitrates coming out in your tap water.  I assume this is one reason why my tap water comes out at 50ppm nitrates!
I agree, Prime is an excellent, well developed product.  Indeed there are many factors that could lead to nitrates present in tap water.  An easy way to see what nitrates come out of your tap is to just test your tap water.  Where I am, I have zero nitrates! 
 
Similarly you could test for ammonia in your water, but I highly doubt you'll get a reading.  If any ammonia is in your tap water as a result of chloramines disinfecting or breaking down, it would not be detectable with standard aquarium test kits.  As a guess, ammonia in tap water would probably be in the range of 0.01 to 0.001 ppm.  API liquid test kits have only 0 - 0.25 ppm as their lowest detectable range.
 
I think that the affect is going to depend on the amount of chlorinated water, the quantity of chlorine, and the tank. Chlorine is an anti-bacterial so it will kill the beneficial bacteria in a tank. Add enough and you destroy the population and send the tank into a cycle.
 
I was sceptical at first so I tested it on some daphnia. I took my 20l tank filled it from the hose no dechlor added and that daphnia colony is still going; I only use water from the hose never bother with dechlor.
 
Depending on where you live, your water source may or may not have lethal, or even dangerous levels of hypochlorite and chloramines.  Conditioning tap water is a very wise precaution that we take to protect our fishies from potentially harmful hypochlorites and chloramines.  If you think your tap water is safe to put directly into your tank because of your experiment with daphnia, that is fine.  I would strongly advice any aquarium owner to treat their tap water.  Better safe than sorry.
 
I have personally done analytical experiments determine what the exact concentration of hypochlorites (in addition to heavy metals).  I'll need to find my journal to give you an exact value since I can't remember it off the top of my head.  I also don't know what the lethal or dangerous level of hypochlorites/chloramines are for fish.  I'm sure different fish have different tolerances.
 
Another thing to note is that small effects of hypochlorite and chloramine poisoning may not have visible symptoms.  For instance, fish exposed to very small amounts of chloramine exposure may not be gasping for breath at the surface, and may not die.  But I think we can assume that inefficient delivery of oxygen to vital organs will effectively reduce their lifespan.
 

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