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Old 06/10/2003, 12:38 PM   #1
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Post Chloramines

In order to understand the mechanism of chloramine removal, a little background information on the chemistry of chloramines is necessary. Chloramines are formed by the reaction of ammonia and chlorine gas. Chloramines can exist as three chemical species: monochloramine (the predominant species found in tap water), dichloramines and trichloramines. The chloramine species depends upon the pH of the water and the ratios of chlorine to ammonia. At tap water pH levels of 7 to 8.5, the formation of monochloramines is favored. Of the three species, monochloramine is the most stable and difficult to remove, as well as the most damaging to aquatic life.

A “ppm-hour” is defined as the exposure of 1 ppm chlorine/chloramine water for 1 hour.
Film-Tec quotes 300,000 ppm-hours (six years at 1 ppm) of chloramine resistance for their TFC polyamide (PA) membrane material, but only 200 to 1000 ppm-hours of free chlorine resistance. This indicates that chloramines will not damage Film-Tec membranes, while free chlorine levels must be held below 0.1 ppm to prevent oxidation damage. The easiest test for chloramine is with a Total Chlorine Test Kit (SpectraPure Part # TK-CL-10). The TK-CL-10 tests for a combination of free chlorine and chloramines. A sample of the wastewater stream from the RO membrane should show no signs of chlorine.

The most important purpose of a sediment filter is to protect the downstream carbon block filters from plugging with sediment. A properly designed sediment filter will have a micron rating smaller or equal to the closest downstream filter element. It will have a gradient density structure such that the outer layers capture the larger particles and the inner layers capture the finer particles. This will maintain a large dirt holding capacity and prevent the finer particles from plugging downstream carbon filters. Using a 5 micron carbon block followed by a 0.5 micron carbon block, maximum chlorine and volatile chemical removal can be achieved without premature filter failure. If a sediment filter is used that passes particles larger than the next downstream filter, that filter will plug, blinding off the active carbon surfaces, reducing its ability to remove chlorine and organic chemicals.

Trade-offs exist in almost any circumstance and carbon filtration is no exception.
The smaller the micron rating, the better the removal capacity due to greater surface area. Carbon block filters made with bituminous carbon are more effective than coconut shell carbon filters for removal of monochloramine. On the other hand, in water supplies with chlorine only, the coconut shell carbon may have higher capacities for the removal of free chlorine and low molecular weight volatile organic compounds such as trihalomethanes (chloroform).

Multi-carbon block pre-filtration is not always necessary, especially in smaller flow rate systems when adequate pre-filtration and sub-micron carbon block filters are used.
Activated carbon will break the chloramine bond and remove the chlorine component leaving free ammonia (NH3+). RO membranes are transparent to dissolved gases that will pass freely through the membrane concentrating in the RO product water.

Generally, reverse osmosis water is slightly acidic, due to the higher ratio of free CO2 to bicarbonate alkalinity. The exception to this rule is the presence of high pH “soda-lime softening” used by some municipalities. Free CO2 dissolved in water forms carbonic acid that lowers the pH to the range of 5 to 6 pH. In low pH RO product water, the ammonia is converted to the ionized ammonium ion NH4+. Downstream de-ionizing resins can then easily remove this charged species. It is cationic and removed by strong acid cation resins (in the hydrogen form) in either mixed bed or separate bed systems. Aquarists can be certain that when salt is properly added to RO or RO/DI water, the expected salinity and pH will be realized.

Charles Mitsis
President SpectraPure Inc.


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Old 06/11/2003, 11:52 AM   #2
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Thanks very much for the comments, Charles.

As you know, there is a great deal of conflicting information on how effective are RO/DI systems at removing chloramines, and whether chloramines themselves could hurt the RO/DI system.

Because of the large number of variables presented by each hobbyist (water pH, starting chloramine level, flow rate, design of the carbon filter, etc.), we have been considering running a survey study of how effective typical RO/DI systems are at removing chloramine under real user conditions.

I couldn't tell from the information on your web site, for example, whether my system will remove chloramine adequately or not (a 7-year old CSP25-DI) in my present setup.

Do you believe that one could make a list of what systems will remove chloramine adequately that will apply to nearly all situations that hobbyists will encounter?

Or will the environmental conditions at each site have an overriding effect on suitability?

Thanks in advance.


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Old 06/11/2003, 01:07 PM   #3
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Thank you very much for this info. There is a lot of chloromine discussion going on right now and everyone has a different opinion. Keep up the good work.


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Old 06/11/2003, 01:14 PM   #4
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hey tony seems as if we are on the right track at least. Thank you spectrapure for I am a proud owner


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Old 06/11/2003, 02:48 PM   #5
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Hi Randy,

Probably the biggest environmental factor in removal of chloramine is the pH of the tap water. At a pH of 8.3, almost all of the chloramine is in the monochloramine form, which is much harder to remove. As the pH level is lowered, the ratio of dichloramines to monochloramines is increased. Dichloramine is very easy to remove by bituminous activated carbon.

The combination of soda lime softening or sodium hydroxide (to prevent piping corrosion) with chloramines is the worst possible condition. The pH is then often in the 9 to 10 range and at that pH, chloramine is totally converted to monochloramine. The reverse osmosis membrane pores will swell by the combination of high pH and free ammonia. This causes very poor rejection of silica and phosphates, and passage of ammonia through the membrane. Hydroxide ions that are present are also very poorly rejected by the membrane so the pH of the RO product water will be high and ammonia laden, creating additional load to the downstream ion exchange resins.

So, to answer your question, there are almost no universal solutions to water treatment. Environmental factors will weigh heavily in deciding how to best treat those individual water sources. I am working on new methods to treat chloramines and will soon have a new cartridge that will better treat most municipal water sources for chloramine removal.

Randy, if you have any questions about your particular water treatment let me know.


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Old 06/11/2003, 03:01 PM   #6
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Thanks.

The combination of soda lime softening or sodium hydroxide (to prevent piping corrosion) with chloramines is the worst possible condition. The pH is then often in the 9 to 10 range and at that pH, chloramine is totally converted to monochloramine.

Yes, lucky me. That is what we have in our local municipal water.

Hydroxide ions that are present are also very poorly rejected by the membrane so the pH of the RO product water will be high and ammonia laden, creating additional load to the downstream ion exchange resins.

My RO/DI water has always read very high (9-10), even post DI. I've never measured it before the DI, and I attributed the apparent high pH to the inability of the pH probe to read properly in the RO/DI water when it had mostly been in tank water.


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Old 06/11/2003, 03:26 PM   #7
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What's your opinion on using GAC's particularly CALGON CENTAUR CATALYTIC Carbon in a 12-40 or 20-50 mesh prior to the carbon block? This carbon claims to remove chloromines from potable water. By using these fine mesh carbons, you will increase the contact time which seems to be important in the removal of chloromines. Not to mention, Calgon Centaur carbon overall seems to be a great carbon. What's your thoughts on that?


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Old 06/11/2003, 06:13 PM   #8
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Hi Randy,

Unfortunately I know of no easy way to treat your water. Our usual solution to this high pH problem with chloramines is to inject hydrochloric acid (HCL) into the feed water to adjust the pH to about 6.0. This accomplishes three things: it neutralizes the hydroxides, converts monochloramines to dichloramines that are readily removed by the carbon prefilters and lastly any free ammonia (NH3+) is converted to the ionized ammonium form. The ammonium ion is well rejected by the RO membrane and in the acid pH range, the swollen membrane pores return to normal with no lasting damage.

But, with a feed water flow of no more than a liter per minute on a small line pressure RO system, an acid injector would cost many times more than the RO system. So what to do?

Nobody likes this solution but when you have water conditions like yours, you have little choice. Fill a 55-100 gallon reservoir with tap water and acidify with HCL to a pH of 6.0. Attached to this reservoir is a high flow booster pump, its inlet flooded, hooked up to your RO system. Operate at 80 psi and all is wonderful. An added benefit to this solution is a decrease in the Langelier Saturation Index (LSI). At this lower pH level, the calcium carbonate will stay in solution and not foul the membrane. The trick is not to concentrate the reject water too greatly so as to precipitate sparingly soluble salts out of solution and onto your membrane. You can also try a concentrate to product water ratio of 3:1 or even 2.5:1 for an improved recovery rate.

If space does not allow you to set up something like this you can add additional stages of DI resins to your system to handle the increased ionic impurities passed on to the DI stages. A two-bed system consisting of a SAC resin in the hydrogen form followed by a SBA resin in the OH form followed by mixed bed(s) would work well but at a greater operating cost.

Charles Mitsis
President SpectraPure Inc.


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Old 06/11/2003, 06:16 PM   #9
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Hi Tony,
Centaur Catalytic carbon is very effective at breaking the chloramine bond. With peroxide numbers below 15, it is 5 times as effective as bituminous carbon at removing chloramines. Since empty bed contact time (EBCT) is reduced considerably, much smaller amounts are needed for equivalent or superior removal rates. We have 10” catalytic carbon filters (CF-CAT ) in stock and total chlorine test kits (TK-CL-10 ) to measure the results. By the way, they are great for hydrogen sulfide removal also.

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Old 06/11/2003, 08:15 PM   #10
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Do you recomend placing it before the carbon block?
BTW welcome to RC, I am glad you made it. We've been waiting for you


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Old 06/12/2003, 10:39 AM   #11
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I though I figured this one out 4 months ago!!

Charles, Are you saying that your chloromine removing cartridge may not be sutable for municiple water supplies? My Ph out of the tap is 8.2


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Old 06/12/2003, 12:17 PM   #12
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Tony,

You will want to place the catalytic carbon filter between the carbon block filter and the sediment filter. The catalytic carbon filter has granular activated carbon and carbon fines that need to be flushed out before hooking up to the RO system. Just put the filter in a housing and run tap water through it, full blast, until the water runs clear.

Stay tuned! I am writing a whole series of articles on reverse osmosis, pre-filtration, instrumentation and ion exchange technologies as they pertain to reef keeping. My next article will be titled, “There is No Such Thing as 0 TDS!” Another interesting one will be a discussion on the so-called 100 GPD Film-Tec reverse osmosis membrane. What it actually is and what it will remove.


Aquaman_68,

I am not implying that our cartridges can’t be used on municipal water supplies, they are specifically designed for that. What I was pointing out was that some municipal supplies treat the water either with calcium hydroxide, calcium oxide or sodium hydroxide to either soften the water or prevent pipe corrosion. When these chemicals are added, the pH will be in the 9 to 10 range and require more specialized treatment. Your tap water pH of 8.2 is within the range of conventional treatment.

Charles Mitsis
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Old 06/12/2003, 01:11 PM   #13
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Quote:
Originally posted by SpectraPure
Tony,
Stay tuned!
My next article will be titled, “There is No Such Thing as 0 TDS!” Another interesting one will be a discussion on the so-called 100 GPD Film-Tec reverse osmosis membrane. What it actually is and what it will remove.
Can't wait, I am behind you 100% on the disscusion of those membranes.


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Old 06/12/2003, 05:27 PM   #14
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Thank you for the clarification

Thank you for the info. I will have to re-check the ph from my tap. I have not checked it since they switched to chloramine treatment


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Old 06/16/2003, 07:01 PM   #15
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Catching up on the questions of the day:

Q.: Can catalytic carbon in a fine mesh form remove ammonia?

No

Q.: Does or can RO membranes remove ammonia?

Yes.

If your tap water is naturally acidic, the membrane will remove ammonia. But, this is not the typical case. Most tap water is above 8.0 pH and some are above 9.0pH. Our usual solution to this high pH problem with chloramines is to inject hydrochloric acid (HCL) into the feed water to adjust the pH to about 6.0. This accomplishes three things: it neutralizes the hydroxides, converts monochloramines to dichloramines that are readily removed by the carbon prefilters and lastly any free ammonia (NH3+) is converted to the ionized ammonium form. The ammonium ion is well rejected by the RO membrane and in the acid pH range, the swollen membrane pores return to normal with no lasting damage.

AND,

As quoted by ichthyman:

Question

How well do FILMTECTM RO membranes reject ammonia and nitrate?

Answer

Dissolved gases like ammonia (NH3) will not be rejected by an RO membrane; however,
NH3 is in equilibrium with the ammonium cation (NH4+), as defined by the following
equation:

NH3 + H+ --- NH4+

Decreasing the pH and/or temperature will convert NH3 to NH4+, which is rejected by
the FILMTEC RO membrane. For example, as long as the temperature and pH are less
than 40°C (104°F) and 7 respectively, more than 95% will be present as NH4+ and the
rejection should be better than 98%. However, if both parameters are allowed to increase,
the amount of ammonia will also increase, accompanied by a corresponding decrease in
rejection by the RO membrane.


Q.: Does a water softener lower pH?

No, water softeners remove calcium and magnesium ions, not HCO3, which is responsible for high pH.


Q.: Also what would the effects on a R.O./D.I. system if a water softener was used for pre-filtration?

Wonderful !!! Again, removing calcium and magnesium from the feed water will increase the life of the membrane. We see all the time, erroneous information that you should never place an RO system downstream of a water softener. This is the preferred configuration for long membrane life.


Q.: Also I would like to know if the catalytic carbon removes ammonia?

Again, NO.


Q.: If they say it removes chloramines then I would have to assume the ammonia is being removed also otherwise I would consider these as false statements.

Consider them as false statements. Catalytic carbon does NOT remove ammonia.


Charles Mitsis
President, SpectraPure, Inc.


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Old 06/26/2003, 12:31 PM   #16
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Charles:

FYI, I measured the total and free chlorine in my system today. The local water company uses chloramine, and the pH is about 9. The total chlorine is about 0.5 ppm in the tap water, with free chlorine less than 0.01 ppm.

Anyway, your unit (CSP25DI) takes out all of the chlorine from the output water (total chlorine <0.01 ppm), and nearly all of it from the reject RO water (total chlorine 0.02 ppm; free chlorine <0.01 ppm).

So I'm happy.


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Old 06/21/2006, 06:49 PM   #17
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well that little discussion convinced me to by spectra pure products, mainly because of the time put into informing all of us of this. and answering these questions.
cant wait for more information. thank you


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Old 06/21/2006, 07:01 PM   #18
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lol, that thread is 3 years old


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Old 06/22/2006, 12:45 PM   #19
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Glad he bumped it. Good read!


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Old 08/07/2007, 12:01 AM   #20
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Bump for an old thread with good info and adding a question.

If going for the bucket type approach. What if you didn't add hydrochloric acid but instead used a product like Seachem Prime or maybe better yet Seachem Safe. This should take away the need of using with hydrochloric acid and it should take care of the chloramines with now bound up ammonia.

Now the question would become. What does this do to the rest of the RO/DI process? Will the problems you mentioned still be a problem even with a high pH of 9+?

Will the addition of Seachem's Safe have an adverse effect on the carbon, membrane or DI cartridges or is this a safe solution to the chloramines and high pH problem?

I realize this could be added after-the-fact in the collection container before using for top-off or salt mix but the objective I'm looking for is to not foul the carbon or membrane and not put a heavy dent on the DI cartridge(s).

Good idea or bad?

Carlo

Quote:
Originally posted by SpectraPure
Hi Randy,

Unfortunately I know of no easy way to treat your water. Our usual solution to this high pH problem with chloramines is to inject hydrochloric acid (HCL) into the feed water to adjust the pH to about 6.0. This accomplishes three things: it neutralizes the hydroxides, converts monochloramines to dichloramines that are readily removed by the carbon prefilters and lastly any free ammonia (NH3+) is converted to the ionized ammonium form. The ammonium ion is well rejected by the RO membrane and in the acid pH range, the swollen membrane pores return to normal with no lasting damage.

But, with a feed water flow of no more than a liter per minute on a small line pressure RO system, an acid injector would cost many times more than the RO system. So what to do?

Nobody likes this solution but when you have water conditions like yours, you have little choice. Fill a 55-100 gallon reservoir with tap water and acidify with HCL to a pH of 6.0. Attached to this reservoir is a high flow booster pump, its inlet flooded, hooked up to your RO system. Operate at 80 psi and all is wonderful. An added benefit to this solution is a decrease in the Langelier Saturation Index (LSI). At this lower pH level, the calcium carbonate will stay in solution and not foul the membrane. The trick is not to concentrate the reject water too greatly so as to precipitate sparingly soluble salts out of solution and onto your membrane. You can also try a concentrate to product water ratio of 3:1 or even 2.5:1 for an improved recovery rate.

If space does not allow you to set up something like this you can add additional stages of DI resins to your system to handle the increased ionic impurities passed on to the DI stages. A two-bed system consisting of a SAC resin in the hydrogen form followed by a SBA resin in the OH form followed by mixed bed(s) would work well but at a greater operating cost.

Charles Mitsis
President SpectraPure Inc.



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Old 08/07/2007, 04:13 PM   #21
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Carlo,

See my PM to you.

Scott
SpectraPure, Inc.


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Old 08/07/2007, 11:09 PM   #22
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I got the PM but must say I was disappointed with the answer of just using:

SF-MT-0.5-10 sediment
CF-0.5-10 carbon
MEM-S-0090 tested membrane
DI-MC-10 MaxCap DI
DI-MB-10 Mixed-Bed DI

Unless I'm missing something ammonia is still going to cause a problem and not all the chloramines are going to get removed.

According to Charles:
"The combination of soda lime softening or sodium hydroxide (to prevent piping corrosion) with chloramines is the worst possible condition. The pH is then often in the 9 to 10 range and at that pH, chloramine is totally converted to monochloramine. The reverse osmosis membrane pores will swell by the combination of high pH and free ammonia. This causes very poor rejection of silica and phosphates, and passage of ammonia through the membrane. Hydroxide ions that are present are also very poorly rejected by the membrane so the pH of the RO product water will be high and ammonia laden, creating additional load to the downstream ion exchange resins."

So being that my tap is at 9.4-9.5 pH the chloramine is found as monochloramine and my membrane pores will swell by the combination of high pH and free ammonia causing very poor rejection of silica and phosphates, and passage of ammonia through the membrane which creates additional load on the DI.

Actually what I see is exactly this on my system. The membrane (tried a few) fouls quickly and the TDS rise after a hundred or so gallons. The DI resins then get used up quite quickly.

Also worth noting is that I've tried this with 1 micron carbon as well as < 1 micron carbon with virtually the same outcome.

I was also kind of taken back that no customer has ever used your usual solution.

"Our usual solution to this high pH problem with chloramines is to inject hydrochloric acid (HCL) into the feed water to adjust the pH to about 6.0."

From reading that posted way back in 2003 it sure sounded like you already had that in place with customers and it wasn't just an "idea".

I'm really disappointed in the "solution" of cartridges proposed as some of my customers are already using the MaxCap system and having the same problems as noted in my PMs and phone call.

Moving forward: I do think the bucket approach is a good cheap MANUAL way to overcome this problem for those of us who go through DI quickly under this set of circumstances. While I myself wouldn't have a problem using an acid I wouldn't want to recommend this to my customers BUT would recommend the Seachem Prime or Seachem Safe or other chloramine detox product in the bucket prior to pumping back into the carbon cartridge.

So my question would be, is using a product like this going to help or hurt the lifespan of the carbon, membrane and DI?

If it's not going to help then it seems like the best approach for me and my customers might just be to remove the membrane (no more waist water or membrane replacements) and use a seperate Cation & Anion stage cartridge. I could then switch out the cartridges for them and recharge them on a rotating basis.


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Old 08/08/2007, 11:05 PM   #23
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I wanted to follow up my last message.

I got a very pleasant phone call directly from Charles this afternoon. We talked for quite a while and he was very generous on providing information and diagnostic tests and things to look for in my present system (not one of his).

It's likely that the chloramines aren't specifically causing the problem with my membrane failure but probably surely aren't helping things. The pH on the other hand is more then likely contributing to the problem but not an end all problem.

He took a good amount of time and told me many different possibilities that could be causing premature membrane failures and gave me a rough idea of how I could go about fixing the problem if in fact it turns out to be that problem. IE excessive aluminum in the tap water. Many of the suggestions would not have led to a sale of any product of theirs. Matter of fact I don't remember any type of "sales pitch" AT ALL.

I'm very satisfied now after talking to him but only wish it was before I had made the previous post so I wouldn't feel compelled to write a rebuttal to my own message.

I NOW feel pretty confident after talking to Charles that the system Scott proposed filter wise would take care of the "typical" problem of high pH and Chloramines that the population at large would have. I just happen to have another problem some where that when combined with these two issues is causing the problem.

So I want to publicly thank Charles for all the information he provided me on the phone which IMHO was way beyond what was called for. KUDOS

Carlo

PS Charles if you can find a few minutes at some point why don't you follow this up with some possible problems like we discussed that some other people might find useful when dealing with membranes not performing as well as expected and maybe a few typical solutions to the problem. I'm sure many others now or in the future will find the information very useful.


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Old 12/11/2013, 12:35 PM   #24
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bump- we are getting hammered by calls on "I have chloramines" what do I do?
Thanks to the Reef Central Community. Great reference for all.
bruce


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Old 03/14/2014, 11:16 PM   #25
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Update on a link to your Chloramine test kit? The link in the above posts is now dead.

Some days, I can smell chlorine in my tap water clear as day. Other days, not at all. I have the SpectraPure 4-stage 90gpd RODI system still using the first included filters. I'd like a little more Chloramine protection, if for nothing else, peace of mind. Do you think swapping out the included carbon block for the ChlorPlus block would be worth it? Or should I buy an outboard canister, bump my DI resin over to it, and run both carbon blocks, then membrane, then to outboard DI?

I know you said local variables are going to play a large role in final outcome. But I don't have a Chloramine test kit....yet. But I recently moved to the area and multiple local reefers warned me right away. Didn't take but a few days before I noticed my drinking water smelling of chlorine.


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