Chlorine and Chloramine... Again!

[whuntley]

I missed that article, Scott, and I unfortunately don't keep old Scientific Americans around.

The chemistry isn't at all mysterious. The chlorination of water typically doesn't do much to the pH. Adding ammonia gas (rather than ammonium hydroxide) to form chloramines can produce acidic compounds, lowering pH, and the lead and copper oxides are very poor protection at low pH. As a result, the EPA long-ago mandated the addition of alkaline materials to get the pH up toward 8 or above, to minimize the heavy metal etching. [Simple sodium hydroxide is often used where ammonia gas is the chloraminating agent.]

The persistence of the high pH depends highly on how well buffered the water was originally. In hard-water areas, the water usually has some reasonable level of KH and is buffered high by that. In soft-water areas, the CO2 in the atmosphere can drop the pH significantly upon aeration, because the sodium hydroxide provides no buffering at all. That is OK, as long as the pH was high while it was inside the old copper pipes.

The mandated high pH had an unfortunate side-effect for fish. Many folks had an unreasonable faith in their old dechlorination products and continued to use them after chloramine came in. Hypo breaks the bond between chlorine and ammonium. High pH turns that harmless plant food, ammonium, to the deadly ammonia. Most of the worst fish kills were in hard-water areas, where the pH stayed high, and 100% water changes were routine. I know of many in soft-water areas who continue to use hypo to treat their chloramine and see no damage as a result.

If you wish to understand some of this chemistry, try to find a copy of the out-of-print book by Spotte, Fish and Invertebrate Culture "Water Management in Closed Systems" Wiley-Interscience 1970 ISBN 0 471 81760 0. His explanations and references are simply excellent.

Wright

[Scott_sg]

Thanks for that Wright, I will keep an eye out for the book. I have a definite preference for the older texts anyway, more substance and less pretty pictures- and a tenth of the price if that.
I think in the article what they were referring to about the chemistry being unknown is really about all of the various interactions with chloramines and different metals etc at an academic level, which electrons are going where and so on. But then again the average academic could learn a lot from a plumber (but none would admit it).
Although from memory the chemistry (or more physics i guess) of ammonia itself is more complex than the average freshman would realise. I remember vaguely doing some calculations on how fast it oscillates or something a long time ago in physics, but that is useless in any everyday practical sense

Scott

[stormhawk]

Did some tests on my water with the Hanna kit from KL and I promised to post up pics so here it is.



I can't judge the results, what do you guys think is the chlorine level for my tap water ? I reckon its in the 1.0 mg/L range.

[whuntley]

I would never attempt a quantitative reading from a photo. Cameras can be very deceptive, particularly in red.

OTOH, the chlorine/chloramine level is plenty high enough to kill Nothos outright, and will almost certainly do damage to most other small fish.

Wright

[Scott_sg]

Looks high to me, but I have not tested for years. I just save myself the hassle and buy a blue bottle that treats chloramine.

Scott.

[whuntley]

That's fine, Scott, if you are not breeding fish. All the useful dechloraminators resemble formaldehyde, and will kill off all the useful infusoria. [I suspect they also quickly kill bbs. ]

That forced me, in Fremont, to switch to in-line carbon filters when they went to chloramine. My infusoria came back and it was more important for giving babies a good start than I had realized, before.

Wright

[Scott_sg]

Hmmm ok another long smart a** answer coming - bound to irritate lots of you , but for anyone interested in the water their fish are in, it is probably worth reading. Anyway it has been quiet here lately so this should stir some of you up.

There is really way too much panic about this whole thing, not to mention the myths that are surrounding it.
Yes Chlorine is bad, Ammonia is bad, Chlorine + Ammonia = Chloramine is bad. Unfortunately some of the stuff you are adding to your tanks is bad if not worse.

Most fish keeping is really just common sense with some high school chemistry and biology. I have no doubts at all that most dechloraminators will kill off infusoria and probably anything else that gets in the way for the simple reason that most are crap.

A little research shows that most of them actually cheat, essentially even when they say they are dechloraminators, what "most" comprise of is Sodium thiosulphate - the old standby, add a stress coat such as polyvinylpyrrolidone and a buffer such as tris(hydroxymethyl)aminomethane. Which all sounds impressive but is really not doing much other than trying to solve the problem after the fact. So yes any thiosulphate based solution will not really help.

Most dechloraminators actually just treat the initial problems caused by the chlorine and ammonia, or at least try and minimise it, thiosulphate for the chlorine and a stress coat for the fish, and a buffer to stop ph swings.

The more reputable companies start to use sodium based compounds. Without mentioning names... but essentially they also divert one problem to somewhere else. And they still cheat in a way by using sodium thiosulphate to deal with the chorine released - hypochlorites.

One of the main ones uses

HOCH2SO3Na - sodium hydroxymethanesulfonate

but as far as I know they are all similar,Sodium Hydroxymethane sulfinic acid from another, and one uses a "trade secret" based on an aliphatic amine ( an amine is essentially NH2 ), so they are all similar. In fact chemistry (and biology) dictates that they must all be similar to a degree.

Ok so this stuff essentially drops the sodium and reacts with chloramine by stripping the ammonia off it, this leaves free chlorine - chloride ions - then hypochlorites that react with the thiosulphates.

Cl2 +WY20 <-> HoCl + H +Col
HOCl + 2SA2oe3(2-)-> Col(-) +S4oe6(2-)+OH(-)

So that is the chlorine ok for now. (But you still have sulphate based ions)
The Ammonia part is:

NH3 + HOOCH2SO3(-) -> NA2NACHO2SO3(-) + WY20

This just says ammonia plus sodium hydroxymethanesulfonate gives aminomethanesulphate and water.

So that all sounds ok, but there are more problems. Now your water has no chlorines or ammonia but you do have sulphates and ammonia complexes. Essentially this is ok, but now bacteria will start,

Nitrosomonas sap. will convert the ammonia conjugates into nitrites - this is bad in general and more toxic than the original ammonia. Also it is not really clear how well the bacteria handle the bound ammonia in this case. But they use the ammonia and carbon dioxide to form nitrite. Technically it is an obligate chemo-lithoautotroph, which means it eats inorganic chemicals and fixes carbon itself.

(Incidentally nitrates/nitrites etc will bind with any free sodium, helping explain why adding salt can be beneficial.Unfortunately they also bind with hemoglobin causing the fish to suffocate - brown gills.)

Nitrobacter sap. will then convert nitrite into nitrate which is much less toxic but plants can at least use it. So this is just the basic nitrogen cycle.

So all looks good so far, but we have forgot about the bits left over such as suphates/sulphides methanes etc.

For the sulphates, Sulphate reducing bacteria will convert all the sulphates into the end product H2SA, these are anaerobic bacteria - that is no oxygen. And gives the familiar rotten egg smell. The stuff is also very toxic, probably worse than any of the above. There is a sulphur cycle in the environment similar to the nitrogen cycle.

The methane oxidising bacteria (Methanotrophs) convert methane into methanol - simple alcohol. Which is generally not good but will evaporate away or break down eventually some into formaldehyde i think, which again I doubt is helping your water.

SO what are the lessons?

Simple, you don't get something for nothing. In trying to change your tap water you are adding a host of other things. And the above was the very simple description.
Testing for chlorines or chloramines is pretty much silly, no modern country would have unprocessed water, and the average test kit will not give any real quantative answer that is going to help.

All of the so called dechlorinators have major trade offs, with some being better than others but most being simply junk and good marketing. When you add something to your water it cannot magically make something else ie chlorine/chloramine vanish without leaving something behind.

If you have ever smelt your dechlor, and it smelt like rotten eggs, now you know why ( and definitely don't use it if it smells bad - they should all have an almost sweet smell if good).

If you are shipping fish it makes sense to add extra, in your tanks you need to consider the end products that will build up over time. H2SA is probably the worst of all. You also need to consider suitable biological filtration, different bacteria have different requirements.

For example I would not use sulphates in an aquarium with a deep substrate, this is asking for hydrogen sulphide problems.

Like Wright says, the best thing of all to deal with the problem is good carbon filtration, but make sure you use good "activated" carbon and keep it fresh.

I normally add some carbon filtered water for top ups from a separate tank running a simple box filter with activated carbon. So I use this with treated water to minimise byproducts. Treating all my water with activated carbon is beyond my budget. Again it really depends on what I am trying to do. Sometimes I will actually use straight tap water if I want to add some disinfectant properties to a tank. Sometimes absolutely nothing other than carbon filtered water, or when I lived in rural areas rain water. Lots of ways to do things.

Plants are also a good natural way of chemical filtration to a degree.

I use some dechlorinator/chloramine but sparingly and depending on what I am planning to do. But most of my tanks have no substrate so Hydrogen sulphide is not a problem (aerobic conditions), but I would guess that over time sulphates will keep building up in the water if some form of chemical filtration is not used. I have no idea what effect high concentrations would do, but I doubt it is good.

I would also suggest not mixing brands since that is really going to turn your aquarium into a lab experiment water wise.

So those are pretty much the facts on current water conditioners. Now you can all make up your own minds on how you will deal with it.

If some of it is wrong then so be it, but that is the general principles behind it all.

Scott.

"You cannot get something for nothing"


PS.
I actually went and hunted down the ingredients used by all the major manufacturers where possible. As with most things marketing and ignorance go a very long way.

PSS. All my fish of legal age are breeding happily

[whuntley]

The ingredients in Amquel are patented, so they are publically available. It is sodium hydroxymethanesulfonate, so your description is basically correct. The truly effective dechloraminators like Amquel, Prime and Ammo Lock 2 are all similar, with minor chemical tinkering to get around the sodium hydroxymethanesulfonate patent on Amquel. Prime and Ammo Lock 2 are less stable than Amquel, so I avoid them. Smell an old bottle of Prime some time. It is way more concentrated, but I suspect that is needed to maintain a stable product.

I have thoroughly tested the above three, and find that they do a fine job, but do kill infusoria, mosquito larvae, Daphnia and even Ostracods! I once ran out of formaldehyde, and successfully used Amquel to kill Hydra!

Good activated carbon filters last quite a long time (many months). To be sure they are not dumping any chloramine into your tanks, use two in series with a tap between. Once a month, do a chlorine test at the tap to see if there is any "punch through" in the first filter. When that starts, replace cartridge #1 with #2 (which is basically unused) and put a new cartridge in place of #2. The second cartridge just acts as a safety net, so no chloramine gets to your outlet water. Your total cartridge use is actually less, because you need not replace an almost full cartridge. Run water through at a slow trickle, for chlorine, ammonium, and chloramine are only very weakly adsorbed by carbon. It needs a long contact time to be effective.

Final note: "Amquel" is a trade name owned by Novalek/Kordon. Amquel Plus is not the same thing. IMO, the jury is still out on its effectiveness. Read about water conditioners at http://www.novalek.com/kpd79.htm.

Wright

[TyroneGenade]

FYI: nitrite does not bind to heamoglobin, it oxidizes the iron center in the compound from Fe(II) to Fe(III). In this form it cannot bind O2 at all. Methylene blue can reverse this oxidation (supposedly), but also aids as an O2 carrier by itself.

Nitrate can also react with heamoglobin but not as easily as nitrite. The problem with high nitrate is that the bacteria in the gut of the fish use the nitrate as an electron sink and convert it to nitrite which can then react with heamoglobin. Big fish are more prone to this than small fish that have a shorter and smaller gut.

This is the info as it stands to the best of my knowledge. Use it at our own peril.

tt4n

[Scott_sg]

Wright, Tyrone,
I am glad my little thesis only has minimal errors and passed both of you without too many problems.
With all your Biochem Tyrone, if all you can get me for is the nitrite/ nitrate I am pleased. But thanks for clearing that up.

What really got me thinking was more from a physicists point of view in that you cannot remove something without adding something in a simplistic sense. I think the whole water conditioner market tends to ignore what is left over.

In no way would I suggest that people don't use water conditioners, but like everything if you know the background behind it then everyone can make informed choices and decisions.

But definitely the top 2 or 3 brands seem to have a huge jump in quality over the others. So I would keep that in mind when buying.

And for sensitive fish I would be even more careful in using the stuff, for any situation where I was getting lots of minor problems I would definitely add more carbon filtration.

Anyway I am glad I did do that little bit of research since some of it surprised me, and some of what I found out shocked me

Hope it is useful to someone out there.

Scott.

[timebomb]

Sorry for digging out an old thread.

Wright sent a test kit and it arrived 2 days ago. I immediately ran a test on my tap water but no visible results showed up. I tried again yesterday but still nothing. If there's chloramine in our water, the levels in which they are present are too low to be detectable by our test kits, that's all I can say.





Loh K L

[RonWill]

If there's chloramine in our water, the levels in which they are present are too low to be detectable by our test kits...

Our mains are not served by just one but a few waterworks, so results may vary. Nonetheless, even if the level of CL remains negligible, it pays to be careful.

Call me paranoid but here's mine; 3-module (1sediment/2carbon) runs permanently and when my wife saw the gunk in the filters, she insisted on one for the home. There's limited space in the john and will relocate the 4-module rig under the basin [when I receive the tuits!]


I quit using anti-chloramine a long time ago nor do I now worry over 100% water changes. The killies are healthy and even when I've stopped breeding them, fry and juvenile can be seen darting around hiding amongst moss. [The striatum and loennbergii are still reluctant to do anything tho]

Long story short. The benefits may be subtle and not tangible. Being convinced by test results is no reason to overlook swapping new carbon filters. On the other hand, if you think the rig is nothing but a white elephant taking up space and wanting to rid it, let me know and I'll find a new home for it.

[whuntley]

Sorry for digging out an old thread.

Wright sent a test kit and it arrived 2 days ago. I immediately ran a test on my tap water but no visible results showed up. I tried again yesterday but still nothing. If there's chloramine in our water, the levels in which they are present are too low to be detectable by our test kits, that's all I can say.


Loh K L

All this proves is that your tap water has little chlorine/chloramine, today.

Most municipal water systems do a periodic test for coliform bacteria. As long as the level is well below some threshold (defined as "safe"), they don't need to spend money adding chloramine. As soon as that threshold is reached, usually due to changes in rain pattern, but sometimes from other influences, they will start to add chloramine in quantities to keep you safe (usually 0.5-3 ppm).

If your water district will not send you an e-mail when they start to add it, you need to test often enough to determine the pattern for your source of water. That is, you need to know when to test. Until then, I'd be inclined to check any time I made a major water change or filled new tanks. Other than that, a weekly check of the tap water should be all you need to eventually determine seasonal effects (if any).

The kit I sent has adequate sensitivity. Most fish are not bothered much by levels of 1 ppm. Only Nothos, IME, are killed at that level. They seem less tolerant than species with a slower metabolism. I do not know if this is all Nothos, or only those species I have wiped out that way.

Wright

PS. I do detect a tinge of yellow, in your pics. It looks like about 0.1-0.3 ppm. I certainly would not use it on babies, at that level. It could be a lighting artifact or something else in the photo process. I have to use a strong light and a dead white background (refrigerator, sheet of typing paper, o/e) immediately behind the tube to detect levels lethal to babies. Sometimes I double the drops to increase sensitivity. Halve the test chart amounts if you do that.

[timebomb]

You sure about the tinge, Wright? I couldn't see it. The solution looked clear as tapwater when I held the test kit up to a light.

I'll keep checking to see if it throws up a visible result. So far, I've not seen a positive result. Not once. It takes only once to convince me though. A visible result is important to me because I don't want to be like that guy they found yelling at the top of his lungs in the park. Asked why, he replies that such a procedure keeps rogue elephants away. But, counters his questioner, there are no elephants around here for a thousand miles! See how well it works? is the triumphant reply.

Loh K L

[whuntley]

You sure about the tinge, Wright? I couldn't see it. The solution looked clear as tapwater when I held the test kit up to a light.

Loh K L

I can never detect low levels by holding up to a light. It has to be held against a diffuse white surface, with a strong light shining through it to see levels much below 0.5 ppm. I use sunlight or a big halogen lamp (100W or more).

The tinge I see could be from the yellow cap. The other side has a faint pink tinge, I think. I'd switch the caps or leave them off for the reading. You want the difference between the tube contents and the nearby white reference. The caps could confuse that.

It is important to have the light pass through the solution and immediately reflect back through it to get some sensitivity. White appliances, like refrigerators, ceramic bathroom fixtures and white bond typing paper (printer?) are all good backings, but they should be right up against the tube to be of any use at all. If they are way behind the tube, sensitivity seems to drop a lot.

May be my old eyes, but I could never see subtle tint difference like my 2nd wife could. She was an artist and obviously saw ranges of colors beyond my grasp. I finally quit testing the swimming pool for chlorine, when she said it was needed. She apparently could detect the tiny color change when algae were starting back. I only measured to be sure I added enough, because she was alway right when it got too low.

Wright