Cycling Problems with QT Tank in Laundry Room - Suspected QAC Contamination

[Tobin VP]

That's honestly just a bad place for an aquarium. You risk contamination from all sorts of chemicals, and the vibrations of the machines will likely stress your fish out. If it was me, I'd be finding another place to put it.

Yeah - its not ideal for sure. I had reservations from the start on the location. A couple of things ...

Saltwater mixing station is nearby and other options for this tank are not great for other reasons.

It is a coral and invert Qt tank. There won't be any fish QTed in this tank. I'm not sure if there is as much of vibration sensitivity for coral and inverts. The vibrational pathways are pretty isolated from the machine to the tank - but there is an audio nuisance as a possibility. Maybe I need to get some accelerometers instrumented next to check/understand.

There is the potential for chemical transfers ... and I'm working to check and/or eliminate that. Hoping to figure out and see if I can pull it off.

 

[Tobin VP]

Welcome to reef2Reef!

This has to be the of the most interesting first posts I've read.

I think the best hypothesis is that some type of amine from laundry detergents, fabric softeners, dryer sheets, etc. is interfering with the test. Some organic amines will do so (although not, I think, true quaternary amines, which cannot go through the chemical reactions for the Red Sea test.

I do not think degradation to ammonia is the likely explanation.

Other ions can also interfere, such as iron, which can give a high false positive.

Using a method like the Seachem alert badges (or Seneye) will reduce some of these interferences.

Thanks. I've been reading more on amine's. Clearly just testing for ammonia with a small amount of fabric softener sheet in saltwater for a few minutes produces a positive result on RedSea test kit. I would assume that this would be the case for all salicylate-based test kits. Not the fault of the kit - but just an interference.

I have a note into RedSea asking for common interferences that they are aware of. It seems to me that anytime a test provides a surprising result it would be helpful to start down the list of common interferences. In some cases this could help discover or diagnose other problems. I hope to get back information from RedSea on this.

I do have a Seachem Alert Badge in the tank. It seems to read better but not truly yellow. I plan to get a Seney soon. BTW - what is the testing method that theses tests use? Has it been published anywhere? Does it measure NH3 directly? I have poked around a bit but haven't found anything.

 

[Tobin VP]

These indicate a more fundamental failure to establish a nitrifying biofilm that can process ammonia without any carbon input. 0.8ppm total ammonia is not a hard challenge for an established nitrifying biofilm.
While it might be tempting to connect this to the interesting positive ammonia results from your laundry room dust, a simpler explanation is that this bacterial product sometimes just doesn't establish a cycle.
Take this example thread:
https://www.reef2reef.com/threads/why-are-all-cycles-not-created-equal.917071/
In that thread, whatever the test kit problems are, side by side the same total ammonia , no2, no3 test kits show that biospira cycled a tank conclusively, quickly, and permanently. MB Start XLM took an absurdly long time to show any Ammonia processing at all (in the absence of carbon).
So it's not necessary to point to whatever compound is in the laundry room dust as a killer of the bacteria. They may just not be very good under no-carbon conditions.
You can either dump in some fish flake, and see if the heterotroph bacteria in MB Start XLM snap to work, or you can pour in some biospira. In either case, I think you'll come to brandon's conclusion. The tank is safe for fish, laundry lint is irrelevant... probably.

Wow! Thanks for this and the link. I have been off learning a bunch.

I'm amazed to see the exact same Brightwell products that I am using show very similar slow/constant ammonia in the absence of carbon and then go to zero. I think adding some carbon to verify I get a rapid go-to-zero response is in order. I will definitely experiment with that upon my return to the tank (I'm away for over a month).

Also, the interplay between autotrophs and heterotrophs and that we start with one but then that possibly the other becomes dominate etc etc is fascinating. I watched this video twice by Dr. Tim:



And I was under the impression that autotrophs were all that we needed from the get go and then we were done. Clearly much more is going on. Another example in nature where diversty drives robustness and that likely we want a little bit of all of it to handle changing conditions or sporadic events. Also, I was unaware to the extent that corals themselves were a big consumer of ammonia (or could be). Thanks for that link.

2. The total ammonia chemistry is slightly reactive to a number of nitrogen compounds, amino acids, proteins etc. Many low-but-not-zero reef results may result from this.

Makes sense.

3. these compounds don't show on the free ammonia films/discs. They use gas-permeable membranes and react to the nh3 in the gas form and thus are a bit harder to fool than the total ammonia tests.

So Seachem Ammonia Badge as well as Seneye work on this principle? Is there a method name for this? I'm interested in looking into this more.

4. I'd wager a bottle of biospira would plow through whatever contaminant is entering through the laundry lint.

You think it would plough through because the biospira in particular would bind with the positively charged QACs? Would biospira be better at this for some reason over others? And if this is the case - is it the general thought this is fairly stable and that over time with water changes you would extract?

6. You'll have a hard time testing for QAC at the low ppm level in saltwater. There are a number of ways to detect them in freshwater though, the strips ought to be fine for this purpose (at a high enough ppm level)

Ok. This is what I found by looking around online.

7. That's within the test error, and would be of no concern anyway.
"Accuracy @ 25°C/77°F ±5 ppb ±5% of reading"
Chlorine/chloramine at that level would be pretty short-lived in a reef system.

Yes thanks. I was lazy and didn't go back to look it up. Thanks for reminding.

(This thread is probably going to make me sample my laundry room dust out of curiosity. )

That would be awesome! If you ever do that I would love to hear the results of one of your super-duper experiments on lint.

 

[Tobin VP]

The oxidation of 1.6 ppm ammonia ( MW 17) only gave 2 ppm nitrate (MW 62). The observed nitrogen mass balance is off. This is a distraction that probably needs clearing up before using the ammonia test result to conclude that the original nitrifying (presumably) bacteria stopped working. A high baseline reading would solve the mystery, though I have yet to think of a readon why the aquarium water would have such a high baseline with the salicylate method.

Great point. Very interesting. So in a perfect conversion we would expect 1.6 * (62/17) = 5.8 ppm ? Which we would then expect to go down over time through other (presumable slower) denitrification mechanisms?

I kept feeling like I should have been seeing higher nitrates. Something clearly is odd here ... but also could be due to process time dependence and when I measured. I will definitely pay more attention to mass balancing in future when cross checking measurements.

 

[taricha]

BTW - what is the testing method that theses tests use? Has it been published anywhere? Does it measure NH3 directly?

yes NH3 directly.
NH3 gas permeates membranes and contacts embedded pH indicators.

see things like this....
Evaluation of pH indicator-based colorimetric films for ammonia detection using optical waveguides

You think it would plough through because the biospira in particular would bind with the positively charged QACs? Would biospira be better at this for some reason over others?

No. "Plow through" because I don't actually think you have a toxic amount of QACs in your tank. And biofilm bacteria are pretty tough.

Basically, if you had a working cycled tank that lost ammonia processing ability after you moved it into the laundry room, I'd think differently about the likelihood of contaminants being important to explain your tank ammonia tests.

That would be awesome! If you ever do that I would love to hear the results of one of your super-duper experiments on lint.

So I sampled some dust around my house.
I found dust that did react with the total ammonia chemistry, to varying degrees, all with a color change somewhere between nothing and the <1ppm color I get from running it on my tap water.
More color response from dust in my living room than in my laundry room.

But none from my bounce dryer sheets.

I also did a couple of tests for QACs, one set with the strips done on liquid, one on the dry dust. Neither the liquid from soaking dust in distilled water, nor the dry dust itself (living room, bedroom, laundry room) showed any detected QACs. Only my QAC-containing lysol cleaner gave a positive result.

This is all consistent with Randy's point that QACs are unlikely to react with the salicylate total ammonia chemistry, but many other things are. Proteins, amino acids, amines, some metals.

 

[brandon429]

In my opinion no forward motion can be attained until someone scores a hach lab nh3 meter and calibrated pH probe + digital temp verified and makes cycling tests. seneye is easier to get than a hach, but the only way to verify seneye patterning already on file is to side test with hach. The only two nh3 meters I know that read in the thousandths ppm nh3


I’m never going to believe non digital cycle claims when digital inspections line up so tremendously in favor of accurate and timely cycle completion vs stalls/ranging outcomes and open ended waits.

once we attain digital logs of nh3 performance data + some type of pattern we can scan among those logs other than seneye, cycling science will be revealed because we will have new data to cross check several years of seneye logs on file like the thread below.

some handy new links for the matter: one of my fav seneye threads. For these reasons:

notice nobody is posting .25 anything, or .2 anything. That’s the measurement realm for non digital, these guys are in the thousandths ppm across systems



notice the tight baseline running across tanks, the timely rebound rates for ammonia control, the repeat ability for bacteria (and plants as Taricha has measured) to instantly take on more work given no ramp up time: multiple large reefs. Varying amount of live rock per tank

Does anyone dose ammonia and/or how would one try?

So, after an interesting discussion on nitrate dosing and looking at my Walt Disney coral and seeing it slightly less colorful than I have seen it in others tanks, I have decided I want to learn about and then try dosing ammonia instead of buying 20 damsels. Nitrate additives I see abound and...

www.reef2reef.com

varying degree of fish and feed bioloading per tank, varying gallons too. All those variables *still align to show reef tanks run .001-.005~ ppm nh3 and even when we test nanos the measures hit dang close to that mark. It’s a universal link, among reef systems, where we can expect to land after a cycle.


that one thread has several clues that fly in the face of conventional cycling rules we repeat online. I’m betting digital measures are about to set some new rules.


instead of a wildly varying ability, there is a hidden skill among cycled tanks only digital testing reveals

So this thread is showing you the inherent nh3 control among a set of random joe reef tanks, AND we get to see actual test loading for once. These guys are spiking liquid cycling ammonia into full running reefs and we watch the ten minutes or less shock absorber ability all display systems have, due to surface area patterns we all copy from one another. If this was a Red Sea thread, it would take those aquarists four days to register the drop back down due to disgusting lag time when compared to digital heh

 

[taricha]

Brandon mentioning hach reminds me that hach also does the salicylate method like Red Sea and API etc, but hach documentation is pretty thorough.
https://www.hach.com/asset-get.download.jsa?id=7639983749

this pdf lists the known interferences for the salicylate total ammonia method. (Better info than red sea)

Some of the interferences listed are the minerals in seawater than cause cloudiness, but don't actually change the color forming reactions much.

(Fun fact, you can learn a heck of a lot about hobby test kit chemistry by finding the hach kit that does the same thing, and reading their documentation.

 

[Tobin VP]

So I sampled some dust around my house.
I found dust that did react with the total ammonia chemistry, to varying degrees, all with a color change somewhere between nothing and the <1ppm color I get from running it on my tap water.
More color response from dust in my living room than in my laundry room.

But none from my bounce dryer sheets.

I also did a couple of tests for QACs, one set with the strips done on liquid, one on the dry dust. Neither the liquid from soaking dust in distilled water, nor the dry dust itself (living room, bedroom, laundry room) showed any detected QACs. Only my QAC-containing lysol cleaner gave a positive result.

This is all consistent with Randy's point that QACs are unlikely to react with the salicylate total ammonia chemistry, but many other things are. Proteins, amino acids, amines, some metals.

@taricha

Wow. Thanks for reporting.

The fact that you got no ammonia response to Bounce dryer sheets troubles me. Of course knowing how precise and experienced you are with this stuff - I'm not questioning that you are correct. But I thought that I was really careful - yet there's still a discrepancy here. As soon as I am back home (unfortunately four weeks from now) I want to repeat my testing on the dryer sheets very carefully.

But a couple of questions:

1. What test kit did you use? (I used RedSea)
2. Did you soak the dryer sheet in tap water? RODI water? Saltwater? (I used Coral Pro salt mixed at standard 34 ppt)
3. Was it an oderless Bounce sheet? (I used Bounce Outdoor Fresh Scented)
3. How much of a sheet and for how long was it soaked? (I used 1/4 of one sheet and soaked for 30 minutes)

Protein, amino acids, some metals - all sound pretty plausible for dust/lint in general in terms of a positive indication (either true or interference). I also think that no carbon in my tank with Brightwell products explains too what I have been seeing based on pat reports. But having you report no response from Bounce sheets makes me want to confirm this for my own sanity.

 

[Tobin VP]

Brandon mentioning hach reminds me that hach also does the salicylate method like Red Sea and API etc, but hach documentation is pretty thorough.
https://www.hach.com/asset-get.download.jsa?id=7639983749

this pdf lists the known interferences for the salicylate total ammonia method. (Better info than red sea)

Some of the interferences listed are the minerals in seawater than cause cloudiness, but don't actually change the color forming reactions much.

(Fun fact, you can learn a heck of a lot about hobby test kit chemistry by finding the hach kit that does the same thing, and reading their documentation.

Thanks! I have the exact same Hach webpages bookmarked and were looking through them a couple of days ago.

I'm planning to contact them about interferences as well as other measuring devices as @brandon429 is suggesting above.

My sense is that rapid automated sampling of ammonia in the ppb range is going to be pricey. Not sure I want to allocate my reef budget into this direction ... but I'm starting to become a little obsessed with cycling dynamics. I would love to get some accurate time series data on this and build some models to understand and verify better. I have done some past work in the area of population dynamics and systems that exhibit these kinds of exponential decay responses that ammonia seems to have during consumption (based off of my own data and many plots I have found online). It would be a very fun project to work on ... and in the end I would hope would be valuable to the hobby.

 

[Tobin VP]

In my opinion no forward motion can be attained until someone scores a hach lab nh3 meter and calibrated pH probe + digital temp verified and makes cycling tests. seneye is easier to get than a hach, but the only way to verify seneye patterning already on file is to side test with hach. The only two nh3 meters I know that read in the thousandths ppm nh3

You may be right. Looking into it further ...

Thanks for that link ... will be studying the ammonia dosing data.

 

[Tired]

Yeah - its not ideal for sure. I had reservations from the start on the location. A couple of things ...

Saltwater mixing station is nearby and other options for this tank are not great for other reasons.

It is a coral and invert Qt tank. There won't be any fish QTed in this tank. I'm not sure if there is as much of vibration sensitivity for coral and inverts. The vibrational pathways are pretty isolated from the machine to the tank - but there is an audio nuisance as a possibility. Maybe I need to get some accelerometers instrumented next to check/understand.

There is the potential for chemical transfers ... and I'm working to check and/or eliminate that. Hoping to figure out and see if I can pull it off.

I would think that a lot of creatures, bones or no, would be stressed by the noise and vibrations. I don't have any scientific way to know that for sure, but I know that noise from motorboats and engines is detrimental to wild reefs, and I can't imagine a washing machine and dryer would be much better. Next time one of them is running, put your hand on the shelf; those machines tend to vibrate the entire room, likely meaning that the shelf vibrates.

As to chemical transfer, I'm concerned about detergent fumes as well as your potential fabric softener issues. There's a lot going on in the air anywhere that laundry is washed, and I'd worry about long-term exposure to small amounts of everything. Again, this is intuition more than actual science, but I've walked into laundry rooms and then had to leave for the sheer amount of smell. If nothing else, I'd expect that sort of thing to be an irritant.

 

[catiebartholomew]

Wow. Im just gonna have to say... "have you tried turning it off and on again?..." oh wait, no wrong problem.

Heres an idea since you went to through the trouble of contacting NOAH about this, maybe not leave it upon the laundry machines where your contaminants are ingressing?

Or if that is too much of an ask, put a lid on it?

The tech data, man where do you find the time.

cycled on may 9th ) i love that graph, thank you. i keep my 75 gal in the garage (where i smoke) and i haven’t had any problems. i think your tank is safe in the laundry room; add glass lid if it makes ya nervous

if you want to ensure your biological filter is intact, dilute like half a drop of vodka into a liter of tank water and then add it back to the tank in a high flow area. make sure you’re running an air stone or a protein skimmer for this (oxygenation is necessary). this dosing of carbon will encourage a beneficial bacterial bloom that will in turn lower nitrates (don’t add too much vodka bc bottoming out your nitrates is like asking for dinos). the bacterial bloom can make your water a little cloudy (skimming fixes this, but so does a water change).

 

[Randy Holmes-Farley]

I have a note into RedSea asking for common interferences that they are aware of. It seems to me that anytime a test provides a surprising result it would be helpful to start down the list of common interferences. In some cases this could help discover or diagnose other problems. I hope to get back information from RedSea on this.

I wouldn't hold my breath for a good answer from red Sea, but here's a list of some interferences in the salicylate method:

Hach Support Online

Your partner in Water Quality - Find expert answers and outstanding support you can depend on

support.hach.com

The Seachem alert and Seneye use diffusion of NH3 across a membrane that excludes charged ions and large molecules.

Although I do not know if the exact details match the commercial products, here's a patent describing the method:

US20080041136A1 - Ammonia detection device and related methods - Google Patents

A reusable device for continuously monitoring gaseous ammonia concentration in a surrounding environment comprising a plurality of layers, including an active layer in which a dye (e.g., an indicator dye useful for measurement of pH) is immobilized to a membrane (e.g., polyamide membrane), and a...

patents.google.com

 

[taricha]

But a couple of questions:

1. What test kit did you use? (I used RedSea)
2. Did you soak the dryer sheet in tap water? RODI water? Saltwater? (I used Coral Pro salt mixed at standard 34 ppt)
3. Was it an oderless Bounce sheet? (I used Bounce Outdoor Fresh Scented)
4. How much of a sheet and for how long was it soaked? (I used 1/4 of one sheet and soaked for 30 minutes)

API, same chemistry as red sea just higher amounts of the reagents (particularly chlorine) to make the reaction proceed faster.
Bounce outdoor fresh scent, pinky fingernail sized piece of dryer sheet in 10mL of distilled water for ~an hour.

 

[Tobin VP]

With respect to my request for information to Red Sea on common interferences, the Chief Scientist just responded with the following:

Regarding interferences, the method is a modified salicylic acid method for measuring TA (total ammonium) in SW matrix. This method may have some interferences from the following components:

Glycine, Urea, Glutamic acid, and Cyanate compounds which could be introduced to the aquarium if you use any supplement containing them.

With regard to the following comment:

API, same chemistry as red sea just higher amounts of the reagents (particularly chlorine) to make the reaction proceed faster.
Bounce outdoor fresh scent, pinky fingernail sized piece of dryer sheet in 10mL of distilled water for ~an hour.

@taricha, Red Sea says "modified" method ... do you have other confirmation that the only difference between API and Red Sea is just the higher amount of same reagent? When I return to the tank in a few weeks I am going to do further testing of the Bounce sheets. I was very surprised that you did not get a positive indication.
The only material difference seems to be the API test kit vs RedSea test kit. Is it possible that the "modified" portion of their test actually changes the chemistry some and additional interferences with Bounce sheets are present when using RedSea? We shall see ...

 

[Randy Holmes-Farley]

With respect to my request for information to Red Sea on common interferences, the Chief Scientist just responded with the following:



With regard to the following comment:


@taricha, Red Sea says "modified" method ... do you have other confirmation that the only difference between API and Red Sea is just the higher amount of same reagent? When I return to the tank in a few weeks I am going to do further testing of the Bounce sheets. I was very surprised that you did not get a positive indication.
The only material difference seems to be the API test kit vs RedSea test kit. Is it possible that the "modified" portion of their test actually changes the chemistry some and additional interferences with Bounce sheets are present when using RedSea? We shall see ...

That list implies that many amines will interfere. There’s nothing special about glycine and glutamic acid compared to other amino acids, and since the list also include compounds like urea the window is wide for the chemistry of possible interferences.

 

[taricha]

The only material difference seems to be the API test kit vs RedSea test kit. Is it possible that the "modified" portion of their test actually changes

Actually, there were a few differences other than Red Sea vs API.
You did 1/4sheet in some volume (100mL?) of water, and I did a pinky fingernail sized piece in 10mL. (likely order of magnitude difference in concentration.)
You let it sit in saltwater and I let it sit in distilled water.
(pH/buffering differences leading to differences in what came out of the sheet into the sample and how much of each.)

The total ammonia kits suffer from both positive and negative interferences from lots of things. I expect something like a dryer sheet contains many of both. How much of each gets into the test sample and what it does in changing the matrix of the test sample all affect how this total ammonia reaction behaves.
I've tested some compounds before that I know have ammonia contamination, but I can't measure it because they contain enough negative interfering chemicals to blank the total ammonia tests out.

Anyway, all that is to say that I am not really surprised that finding a modest ~1ppm sized reaction in the ammonia test from a product with many ingredients that could positively or negatively interfere could look different when it's done under slightly different circumstances.

@taricha, Red Sea says "modified" method ... do you have other confirmation that the only difference between API and Red Sea is just the higher amount of same reagent? When I return to the tank in a few weeks I am going to do further testing of the Bounce sheets. I was very surprised that you did not get a positive indication.

I'm not going to say I know completely the components of each test. I know each relies on the same well-studied reaction. Here is a google books link (click on the link to p188) to the section on the ammonia method in Grasshoff's Methods of Seawater Analysis.

API delivers more reagants, including about 4x the hypochlorite, Red Sea includes a chelating agent (the powder scoop) that almost totally prevents precipitation from happening in saltwater - this is probably their "modification". Red sea also delivers the reageants in a different order. API doesn't try to avoid precipitation, so it runs the reaction at higher pH to go faster. None of this really changes the story from "attempting to do a hobby ammonia test on water from a dryer sheet gives results that are difficult to interpret, due to known and unknown interferences."

 

[brandon429]

Tobin soon it would be ideal to watch your system carry life, it's ready for that. change all water leaving behind functional bioslicks/reinstate all clean water and plop some fish in there lets watch them live.

if I had to pick a meter to base water changes from it would be a seachem alert badge. Cheap, does misread, but lowest instance of all the myriad misreaders that have plagued stalled cycling threads for two decades. if your tank was a display, I'd advise to never run an ammonia test kit again on it then I would advise that once more for good measure. in a limited surface area qt, torture yourself away lol. alert badge is what I would use. cheap. pretty reliable on the thousands Ive seen. a few misreads, not many.

specifically by misread I mean threads where an alert badge is alerting, yet the display pic is a pic of a full blown reef clearly running well. we get those nearly daily on non-alert badge, non-seneye posts as the clear pattern I'm seeing.

In 100% of instances, a pic of a normal looking normal running display tank reef is not in ammonia distress unless there are unstated dead fish littered about and hidden from the pic view. who does that in reefing, tank pics of a display are a fine troubleshoot to ammonia issues especially when the only other option are test kits tripped up by amino acids.

B

 

[bnord]

First post here on R2R! … I am new to the hobby but have been reading/studying it for years. I finally have space at home to begin. I will be following up in the future with build threads for my salt water mixing station, QT tanks (invert and fish), and display tank that I’m still building. I’m excited to finally post after 100s of hours of only reading.

I am having problems fishless cycling my coral quarantine tank - and it seems that I am possibly in a stalled cycle state. I have tried various substrates over the past 12 weeks and have monitored tank parameters almost daily. I have narrowed several things down and now suspect that Quaternary Ammonia Compounds (QACs) from fabric softening dryer sheets (standard Bounce Outdoor Fresh scented) have been transported into the tank through lint settling in the air. I want to get a read from the expert community if I’m on the right track here and I also want to understand the chemical mechanisms that could be at work.

Here are the details:

Tank Setup​

My coral QT tank is located with my salt water mixing station in a laundry room (Figure 1). This tank is a 10 gal Fiji Cube (7.6 gal of actual water volume) and is bare bottom with no rock. Initially upon filling the tank I used 18 MarinPure Biomedia 1.5” Spheres as a substrate, Brightwell MicroBacter QuickCycle as my ammonia source, and Birghtwell MicroBacter Start XLM as my nitrifying bacteria source. My salt mix is Red Sea Coral Pro and I use all Red Sea test kits. I should also note that I use a 7-stage BRS RODI filter system and have confirmed zero TDS in my RODI output water. I also verified less than 1 ppb Total Chlorine with Hanna Ultra Low Range Checker in my RODI water. (NOTE: My tap water is 40 ppb total chlorine. My water utility is clearly using chloramines).

Figure 1: The Coral QT tank in Laundry Room.

​

First Tank Cycle Attempt​

I was hopeful for a fast 10-day cycle but was also aware that small bare bottom QT tanks are notorious for needing more time and patience due to a lack of suitable surface area for the bacteria to take hold. It took nearly a month to cycle the tank. I took detailed readings of total ammonia, nitrite, and nitrate daily (see Figure 2 below). The shape of these curves for the most part tracked “typical” production and decay trends. At the completion of this month long process the total ammonia was reduced from 1.6 ppm to very near (but not quite) zero total ammonia (< 0.1 ppm), nitrite had spiked at 0.2 ppm and then disappeared, and I was at 2 ppm nitrate. After almost a week at this non-zero reading of < 0.1 ppm, I assumed that I was having difficulty reading zero precisely with my test kit. It seemed like the tank had for the most part cycled, but I wanted to be sure and test that before introducing livestock.

Did the Tank Cycle?​

I wanted to double check and test the cycled tank by simulating some bioload before adding any livestock. I added a small amount of QuickCycle (estimated to be a typical couple of days of bioload for a fish system of this size). This took the TA to 0.8 ppm and I expected to see it consumed within about a 24-48 hour period. Unfortunately, there was little to no response at all - I then kept supplementing with MicroBacter Start XLM and it brought it down over the course of a couple weeks. During this time it seemed like it was the bacteria dosing in the water column that was doing the work. It finally settled again at about 0.1 ppm this time a little higher than before. In retrospect having it spike to 0.8 ppm was a bit high for a 2 day bioload ... but even in this case it didn't feel like it should have taken 2 weeks with multiple supplemental bacteria doses to bring ammonia back down (these dosing times are not denoted in Figure 2). It didn't seem like the tank had cycled and I was worried that the reason the ammonia ultimately came down was due to my continued dosing of the bacteria and not because I had established a suitable microbial biome.

Attempting a Re-cycle with more Substrate​

Next I decided to do a 50% water change and then I removed my substrate (18 MarinePure ceramic bioballs) from the sump area to move into display area where I could visually examine if biofilm was forming on the media. The ceramic bioballs were in a filter mesh bag for easy removal. At this point I was shocked to find a strong biofilm coating on the entire outside of the bag. This is a good sign - right? But then I placed it in the display area and it floated! The entire bag floated with ceramic balls. The biofilm on the outside of the bag was so well formed that it was encasing the bag and sealing gas inside of it and it actually floated the bag. This was surprising to me (can someone else confirm ever seeing this?). At this point I realized that I was clearly not getting much flow into the bag where the balls were and because it was sealed off it likely was a pretty anaerobic environment. So the tank was not benefiting from the massive surface area of the media itself to grow beneficial bacteria. I started wondering if possibly I had too low of surface area for the beneficial bacteria to cycle my tank. At this point I decided to switch to the Brightwell recommended Lattice Nitraz and much more porous filter bags. I put in 2-3 times the recommended amount of Lattice media and filled the rest of my sump with 20 plastic bio balls (older technology but many experts swear by it for aerobic uses). I introduced them slowly over many days as I removed the MarinPure bio media balls and agitated them before removal to slough off as much beneficial bacteria into the water column as possible. I also re-dosed MicroBacter Start XLM all over again in an attempt to reseed the beneficial bacteria in the other media. At this point it seemed that I had plenty of the bacteria present in my tank.

I then added a couple of drops of QuicCycle to simulate a bioload to see if the tank would consume the ammonia. TA immediately spiked this time at 0.6 ppm and stayed there for over a week. Then it began going up! Wait! TA going up with no livestock? Something was wrong here. Over the next few days the TA reached 0.8 ppm and was there for several days. I continued to add supplemental bacteria and it did then go down over the next several days and this time the TA leveled off at 0.3 ppm - well above zero. At this point it felt like once again I had a stalled tank. I still had ammonia. I had helped bring it down with additional bacteria dosing but It was (and is still) stuck at TA of 0.3 ppm.

Figure 2: Cycling Data: Ammonia, Nitrite, and Nitrate over 12 weeks. Initial cycle and two subsequent stalled tests shown. There are a couple noisy/erroneous readings that are apparent in the data). Times of bacteria dosing not shown.

Finding the Problem - The Investigation into QACs​

At this point I concluded that I either a) I had another ammonia source in my tank, or b) my TA readings were wrong. First, in order to investigate I wanted to eliminate faulty readings. I made up several precise salt water batches and through several checks of my testing kits (I have multiple Red Sea kits) I got very consistently zero TA readings on these batches across more than one kit. I should also note that the other previous non-zero TA tests described above were reproducible - in many cases I double tested them. I convinced myself that the test kits and my use of them were not at issue and I was able to test zero TA with them.

I then turned my attention to possible ammonia sources and thought that it could be introduced through the air. I first looked through the tank for any large bugs or any other organics that might have fallen into the tank but I found none. Recall, that this tank is in a laundry room and I next focused on this and especially on the chemicals in the room. The laundry detergents in use (sometimes containing bleach) are kept far away from the tank - but is it possible that bleach could transport through the air? This seemed unlikely but I wanted to rule it out. I also considered the fabric softener dryer sheets in use as there is a lot of dust (i.e. lint) that forms on horizontal surfaces in the room. (Note: There are a couple existing discussions on R2R about tanks in laundry rooms but there is nothing conclusive in those threads on the associated risks.)

I purchased the Total Chlorine ULR Hanna checker and got 5 ppb TC in the tank. This was higher than my target of keeping it below 2 ppb as I found some articles suggest this level for marine environments. Recall, I get 1 ppb TC out of my 7-stage RODI so the in-tank readings showed additional TC over the source RODI water. This 5 ppb TC reading was concerning since it was clearly above the suggested safe levels. It was (and still is) not clear what impacts this has on the tank, but my focus moved quickly to fabric softeners since what I found was even more concerning.

I mixed up a precise batch of saltwater and confirmed zero TA in it. I then pulled a small amount of lint from the lint trap in the dryer, soaked it in 100 ml of this saltwater for a few minutes and then tested for ammonia. I got high levels of TA at nearly 2 ppm (this test not shown in figures). I then went around the room and collected small amounts of dust (with a wet finger) from the tops of picture frames on the walls and transferred this dust/lint into 100 ml of salt water … this too tested high for TA at 0.8 ppm (shown in Figure 3). This testing was to discern the presence or lack thereof of ammonia in the lint/dust and it showed that it was clearly present and at levels that surprised me relative to the small amounts of lint that I collected. I did not control for the precise amount of lint/dust dissolved into the water in each test case … but it was on the order of the amount that could easily settle into my tank over several weeks. This experiment clearly showed this transport mechanism as a viable ammonia source.

Next, to confirm the dryer sheets as the source of the ammonia on the lint specifically, I took a small fragment of a Bounce dryer sheet and soaked it for a few minutes in saltwater and again found high TA at 0.8 ppm (see Figure 4). It appeared to be at least in part the Bounce fabric softener sheets in use with the dryer. Note too that dryer sheets transfer a chemical coating to fabric through the sheet being heated. In this case the sheet fragment was not heated which would likely transfer far less QAC out of the sheet and into the saltwater as compared to what would occur in the dryer. I then did some research on fabric softeners and I found that almost all of them - as well as many many other things in our home environment - contain Quaternary Ammonia Compounds (QACs). I looked up the “smart label” data (detailed listing of ingredients) online for the Bounce sheets and one of its primary ingredients is Dialkylester Dimethyl Ammonium Methosulfate. Moreover there are some 52 other compounds that create “fragrance” in these Bounce sheets. Yikes!!! I'm not a chemist … but they all have scary names that only chemists can pronounce ... I would think no one would want any of them in their tank! I sure don't.

Then as a follow up test, I extensively cleaned the lint trap of the dryer and ran 5-6 loads of laundry with NO dryer sheets but still using typical laundry detergent in the wash cycle prior to the drying cycle. I then collected this lint from the lint trap and again mixed with my saltwater and tested TA. I was surprised to get almost zero TA at 0.1! Note I was not able to perfectly clean the entire inside of the dryer and expect over time that this would diminish even further. The prior lint when using dryer sheets appears to have contributed all (or at least most) of the TA in the prior readings. Now that I had removed the use of Bounce dryer sheets the resulting lint in the trap (and therefore likely the lint in the air) were clear of ammonia.

Figure 3: Total Ammonia readings after cleaning lint trap with no Bounce sheets and dust/lint from room. The dust/lint vial was collected from the tops of picture frames in the room - this dust settled when Bounce sheets were still in use prior to lint trap cleaning. RODI control (TA=0ppm). Lint from dryer trap after cleaning (TA=0.1 ppm). Dust/lint in room (TA=0.8 ppm)

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Figure 4: RODI and salt water mix control (TA=0 ppm). Fabric softener fragment (TA=0.8 ppm). Tunze Care Panes cleaner (TA=1.2 ppm). Note that specific magnitudes were not controlled for, rather these tests showed the presence or absence of ammonia indication only.

QACs in Tank​

Based on these tests I am currently concluding that a significant amount of lint over time (in this case many weeks) was transported into my QT tank by settling through the air. Furthermore, during the time that Bounce dryer sheets were being used in the dryer (almost daily over many weeks) this lint was coated with significant amounts of QACs. It seems that initially the tank may have cycled but during and towards the end of that time enough QAC was accumulating that I lost the cycle - or at a minimum the cycle was fine but the tests possibly wrongly indicated the perpetual presence of ammonia. Over the last two months the baseline ammonia of the tank has continued to increase and it was not until I removed Bounce sheets that it seemingly has plateaued now at TA 0.3 ppm. Coincidence? Possibly. But at this point I have no better working hypothesis for the TA readings in my tank.

In addition to the possible introduction of ammonia into the system, there also appears to be a lot of other reasons that QACS are not good for aquatic life and I have found many technical papers that list QACs as such. I also recently spent (too many) hours reading about the infamous Vibrant situation where polyQACs are apparently involved as well. It is clear that QACs are bad in many ways.

At this time it seems very feasible that QACs in signifiant quantities were transported into the tank. The only way I can positively confirm this beyond a shadow of doubt is to directly test for them. I'm looking into these testing options and any ideas on reasonably priced ways to conduct them are welcome. It is not clear if online services will/can test for QACs.

Current Course of Action​

My current course of action at this point (pending better advice) is to do a 100% water change, complete cleaning, and start again with NO bounce sheets in use in the laundry room. Furthermore, as a precautionary measure, I am planning to add a desktop air purifier to the room near the tank to further extract lint/dust from the air.

But in the meantime I want to get any comments from the community on this 12-week adventure I have been on. Am I missing anything here? Also I would love to get some expert QAC chemistry explanations on the possible mechanisms that would be at work here and if high(er) ammonia readings would be consistent with the presence of QACs.

Questions ​

1. Does the conclusions that QACs are likely the culprit for high TA readings and the inability to cycle make sense?
2. Is it possible that the QACs are just a positive interference in the salicylate-based test kit? Like iron or copper typically are? For example, is it possible the QAC R groups are stable in the tank but are broken down during the testing methodology (introduction of reagents) and thus depending on pH convert into NH3 and NH4+ only in the test vial?
3. Is there really ammonia being introduced? I read that QACs (at least on some test strips) do not register in TA (but those test strips may not be salicylate-like). Is it possible that only ammonium NH4+ and not free ammonia NH3 is being introduced? And would that even really matter since it would eventually be present for conversion? Note: I have a Seachem Ammonia badge in the tank that always seems to register lower free ammonia than the Red Sea tests would indicate (after pH and temp correction lookup). Admittedly a visual badge of this nature is not super precise and I can not confirm if these badges directly measures free ammonia or if it is simply inferred on the badge through actually measuring total ammonia. This is an anecdotal observation that keeps my attention and makes me think positive interference is a possibility within the test kit.
4. Is it that the QAC level will not allow beneficial bacteria to survive or at least at a minimum not allow it to thrive to the extent needed for ammonia reduction?
5. When I restart/recycle the tank would it make the most sense to dispose of all Lattice Nitraz, plastic bioballs, and MarinPure spheres? It seems like it is possible that QACs as a cation could possibly remain attached to the medium?
6. I looked into inexpensive test strips where I could test for QACs. The food industry uses these, but I could not find any confirmation that they are accurate in salt water at the pH levels we operate in and it is not clear to me what precision I would even need to assess reef safety. Any insights here are welcome.
7. My total chlorine did go up from 1 ppb to 5 ppb within the tank. Would QACs possibly do this? Or do I have another possible contaminating source of Chlorine? What levels of Total Chlorine would you consider bad in a reef environment?

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Additional Observations​

1. I am leaving the tank up for another 5 weeks as I go on a long vacation with an ATO operating and some remote monitoring capability. I am curious to see if there is any recovery at all of this situation. I expect that the QACs will not degrade on their own and I will continue to see the non-zero TA readings after 5 weeks. But the point here is that I still have access to the current water chemistry in the tank if anyone thinks I could conduct further testing on it.
2. I would have loved to see a Seneye in tank during this process. I'm thinking about getting one when I restart and recycle the tank. I suppose it could be useful to me later as I take fish quarantine tanks up and down and possible hospital tanks.
3. I have also been dosing magnesium, alk, and calcium via Red Sea Foundation elements. I have been pulling my hair out with low alk readings regardless of how much Red Sea Foundation B I dose. I have even conducted a pause and then ramped back up slowly as Randy Holmes-Farley suggests in one of his online essays. The original Coral Pro salt water mix was confirmed to be 11.5 dKH when the tank was filled as well as on the subsequent 50% water change. This tank quickly goes to 6-6.3 dKH regardless of my attempts at correcting it. I have stopped trying as I just continue to get calcium carbonate precipitate and have had my return pump seize. My Mg is staying at 1350-1400 ppm and Ca at 420-460 ppm …. and notably the Ca is getting consumed (albeit more slowly) as the CaCO3 forms. Also, I have read Randy H-F’s explanation of Mg(OH)2 formation as a cloud when dosing. I dose into strong flow to limit the amount of time there is a high pH environment at work … but right after the magnesium hydroxide cloud starts to dissipate (about 2 secs) I see a clear precipitate form in the water column where the cloud was … it looks like snow (some fairly large flakes). This swirls around for a while and I am not sure if it goes back into solution or settles. What is this? I didn't think CaCO3 could form that fast in the water column itself. This is an odd effect that I could not find an explanation for. At this point I wonder if it could be related to the presence of the QACs? Is the inability to keep higher alk levels possibly consistent with the presence of QACs?
4. I have had a Neptune Apex in the tank for a couple of weeks. The ORP has never exceeded 170-185 mV which is very low. I know that many people discourage paying too much attention to this parameter, but would low ORP be consistent with the presence of QACs?
5. I use Tunze Care Panes to clean my aquarium glass. I'm very cautious not to get any of it into the tank. But I did do a test on a small amount of it on a rag and then soaked in salt water and it resulted in incredibly high TA readings. I had several email exchanges with the company and their product engineers. They even provided me with the MSDS and assured me that all ingredients are "natural" botanical oils, water, and alcohol and that it is impossible for any ammonia or QACs to be introduced from their product. Their only suggestion is that some ingredient in their product, while safe, could be a positive interference on the salicylate method.

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Ramifications and Ideas Going Forward​

I'm surprised to find how prevalent QACs are and how (seemingly) easily they can make their way into our tanks. Moreover, there have recently been researchers expressing concern about the increased use of disinfectants of all kinds due to COVID-19. These disinfectants often times contain QACs. Also, there are supposedly more than 200 commercial product categories that contain QACs - air fresheners, detergents, disinfectants, fabric softeners, etc. There are many potential sources: A cleaner or air freshener sprayed in the room? Disinfecting your hands with anti microbial lotions/cleaners and then shortly after working in the tank? Fabric softener laden lint in the air? The list goes on.

At the same time I have noticed a large cluster of unexplainable system crashes and stalled cycles in the online forums that seemingly go unresolved. User brandon429 seems to have great passion on this topic and he has done a great deal of work in this area. He even has come up with an approach to confirm the presence of a cycle by looking for movement in the readings - effectively by removing/ignoring any constant offset of ammonia. It indeed is a very clever approach and would be consistent with accounting for a positive interference in the testing methodology (possibly QACs) that are offsetting results in a reliable deterministic fashion. The fact that fish and coral are living/thriving in these ultra high ammonia cases makes one conclude that the tests are clearly wrong. But maybe it is more nuanced than that ... maybe the tests are just being used in an environment which have positive interference. Are QACs possibly involved more than we realize in these situations? And this brings me to the last point/idea.

If the expert community thinks that indeed QACs in my case are responsible for my high ammonia readings then either the QACs 1) destroyed the bacteria that was needed, 2) acted as a positive interference in the testing, or 3) introduced ammonia into the tank. Or possibly all of them in various combinations? But regardless, under any of these cases - if an aquarist sees unexpected ammonia spikes - or the presence of baseline ammonia in the system that is otherwise unexplainable - does this represent a possible surrogate indicator for QACs (or other interferences)? A so called "Canary in the Coal Mine" for the possible introduction or build up of QACs in our tanks? If so then follow on testing would be warranted which also suggests the need to have affordable ways to measure QACs in our tanks at the concentrations of interest.

Closing​

Thanks to those who read this far! Admittedly, this was a VERY long (first) post here on the forum and hopefully not too overly detailed. I have been on this adventure for a few months now and wanted to provide as much detail as possible and then get the community's thoughts.

Although the last 3 months have been frustrating as I attempt to cycle my first tank - I’m super excited to be entering the hobby. I have always loved technical challenges … and clearly this hobby has them! Can't wait to actually buy some coral and fish some day!

Wow - my first response to your outstanding write up as a head of a vaccine research and development team is - if you ever need a job, i would like to talk to you
2nd is, i do not allow any cleaning products in hte first room, just water and vinegar - and you have brought your tank into the cleaning room

 

[D3DPrintedThingz]

ps

I love huge initial posts I too am an over typer heh

Hahaha I can also attest to this Brandon fixed me right up, I was “cycle questioning” myself not long ago, and was extremely quick to help. Dude knows his stuff!!!!!