O zone question

Randy Holmes-Farley

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But if you continue to pump gas (ozone) in, then gas has to exit the closed system somewhere, or else it would continue to build up, right? Unless by recirculating, 100% of the gas introduced completely dissolves into the water and exits with the water?


Ozone rapidly becomes not a gas once dissolved into seawater. It reacts with and quickly becomes other, reactive chemicals, such as hypobromite:

When ozone is applied in seawater in concentrations higher than are naturally present, a larger variety of chemical reactions take place. Chief among these is oxidation of bromide to hypobromite:6,7

O3 + Br- --> BrO- + O2

BrO- + H2O --> BrOH + OH-

The first reaction is very fast, and the half life of unreacted ozone in water with a lot of bromide (such as seawater) is on the order of a few seconds.8 Because hypobromous acid's pKa (in freshwater) is about 9, it is primarily in the protonated (uncharged form) in seawater, but a significant amount of BrO- is also present.3 The hypobromous acid is itself a strong oxidizer and can rapidly oxidize other organic or inorganic materials.4

The hypobromous acid can also react in a variety of ways (including disproportionation and additional oxidation with ozone) to form bromate:

BrOH --> --> --> BrO3-
 

LobsterOfJustice

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Okay, that was my main question. So by sealing air exits from the reaction chamber, it is possible to force all the gas introduced into solution and then only have to deal with treating the water effluent.

Randy - since I have your attention - why did you eventually discontinue use of ozone? I have recently re-read your three part series in the past week to refresh myself on the topic.
 

Randy Holmes-Farley

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I'm not sure you can force it all into solution in the time you have in a typical reactor. I could smell it in the effluent of my reactor.

I stopped largely because I was having HLLE types of issues on tangs (fin deterioration on a yellow tang, HLLE on a hippo tang). Not sure if it was the Marineland Black Diamond carbon I was using, or the ozone (both have received comments that they contribute), but after I stopped both (moving to ROX GAC), I didn't have the problem on future tangs.
 

shiftline

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Carbon actually can be a cause?!

Randy - how much ozone #/mg to what size of system did you have the ozone on?
 

jason2459

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https://www.reef2reef.com/threads/any-ops-on-decent-activated-carbon.270448/#post-3245038

I look for acid washed.


BRS lignite is ok. Rox is better. The filter guys GAC. TLF hydrocarbon is good along with seachem matrix. ( I believe it was highlandreefer from another forum that had a great breakdown on GAC. Old thread. Edit: It was boomer but highlandreefer was involved as was Randy as well)

Edit:

Rinse well but not forcefully, do not crush, and do not tumble.


Edit edit edit edit: Here it is, one of my favorite threads discussing GAC

http://www.reefcentral.com/forums/showthread.php?t=1231262&highlight=rox+8



https://www.reef2reef.com/threads/h...change-your-carbon.280614/page-3#post-3408084

Actually, it's gone past anecdotal. Use low ash, acid washed, high quality carbon thats rinsed well and not tumbled.


Start with the link I linked to in this post.

https://www.reef2reef.com/threads/any-ops-on-decent-activated-carbon.270448/#post-3245038




And there's these

http://www.advancedaquarist.com/blog/activated-carbon-affirmed-as-causative-agent-for-hlle-disease


http://www.advancedaquarist.com/blo...ted-in-inducing-head-and-lateral-line-erosion



And from Boomer's comments to the affirmed article


Boomer

5 years ago

The theory was small sharp <carbon> dust particles would get into

lateral line and bounce around because of the hair cells causing the

erosions and subsequent fibrosis."


This is not new news, it has been mentioned many times in the last 20 years, about participles getting into the neuro masts. Researchers keep for getting that many do not get HLLE, even when using massive amounts of GAC. You are NOT suppose to be allowing the GAC dust to get into the tank, good pre-rising usually stops this or using a filter floss at the output. And not ALL HLLE is from GAC.


Lastly, this new article by M. Andrew Stamper are some of his findings from 2 years ago, as I have posted them on fourms


A couple of observations on this complex issue.


We are currently putting the finishing touches on a manuscript

describing the dynamics of HLLES in ocean surgeons housed in water

polished with carbon. We are aiming for the Journal of Aquatic Animal

Health.


• Ed Noga’s group has proposed to talk about a HLLES as a

depigmentation clinical sign instead of a syndrome…Corrales, J; Ullal,

A; Noga, EJ Lateral line depigmentation (LLD) in channel catfish,

Ictalurus punctatus (Rafinesque). Journal of Fish Diseases. Volume 32

Issue 8, Pages 705 – 712.


• It is important to note there are possibly two phenomenon happening which are being labeled HLLES.


o One phenomenon affects the lateral line which takes two forms.


o One affects the neuromasts within the lateral line-has been documented with heavy metal toxicity.


o One causes an erosive “dermatitis” also known as Chronic Erosive

Dermatopathy. We have found this version with the use of activated

carbon and ozone.


 Baily, J E, Bretherton, M J, Gavine, FM, Ferguson, HW, and

Turnbull, JF. 2005. The pathology of chronic erosive dermatopathy in

Murray cod, Maccullochella peelii peelii (Mitchell) Journal of Fish

Diseases 2005, 28, 3–12.


 The second phenomenon is known as “epithelial thinning” which is

caused by high levels of cortisol…ie stress (multifactorial). Ed

Noga’s group describes this in…Udomkusonsri, P., E.J. Noga and N.

Monteiro-Riviere. 2004. Pathogenesis of the Acute Ulceration Response

(AUR) in hybrid striped bass. Diseases of Aquatic Organisms 61:199-213.


• Telling the difference….


o HLLES-Erosion starts at the pores and increases until they coalesce and the erosions blend to make a bigger ulcer.


o Thinning happens over a larger generalized area. Where the

epithelium starts to become transparent and eventually thins to a point

where an erosion takes place eventually resulting in an ulcer.


• We don’t know why the epithelial thinning and HLLES has a higher

affinity for the facial region. We do know there is a significantly

higher population of goblet cells within the facial and lateral line

regions of ocean surgeons. We are currently looking at mitochondrial

populations of the cells in these regions to see if they have a higher

energy need and may be more susceptible to electron disruptions.


• Current controlled experiments using ocean surgeons:


o Coconut carbon has been repeatedly used at different main stream

and side stream experiments. It causes very predictable HLLES in full

stream as well as side stream which keeps the TOC below 0.5 ppm. Very

little HLLES develops in the same side stream experiment where the flow

is reduced allowing a 1.0 ppm TOC.


o HLLES develops in fish housed in water exposed to ozone but ORP

of the environmental water at around 320 mV (no net oxidants compared to

control systems).


o There have been two vitamin deletion studies with controls (Vit A

and C) performed by the University of Florida. Vitamin A was negative.

Vitamin C was equivocal and needs to be rerun.


o In-line UV did not cause it.


o In-line foam fractionation did not cause it but this experiment needs to be rerun.


o Metals-Application of carbon had no significant manipulation of

metal concentration. No significant difference in aquarium tanks that

had HLLES verses ones that did not.


HOWEVER…on open question is the speciation of metals available to the

fish…One thing in common with ozone and carbon is the manipulation of

DOCs. Carbon absorbing it until it the carbon is saturated and ozone

chewing it up into smaller molecules. Is it possible that metals may

be more toxic in these environment (i.e. toxic enough for these cells

but not being overtly toxic) because they are not bound by the DOCs.

This is a very complex question and is cost prohibitive to investigate.


• Carbon Dust-Our later carbon studies had 1 micro filters in-line

(post carbon). Histopath did not show any carbon particles within the

tissues. Another thought is there are plenty of silicates (diatoms) in

the water which would be more affective source of irritants. Carbon

dust would provide a large surface area for absorption but I am not

convinced it acts as and irritant.


• Weight of fish per gallon…a ratio of 2.4 grams of fish/gallon

(when the fish reach 30 grams and start to show breeding colors we

average 6 fish/75 gallons) seem to keep most of the social stress at

bay. We controlled for social structure to make sure this was not

causing any HLLES signs.


• Healing of lesions during these experiments…Most of these

experiments are a yes/no question. If using controls you can tell if a

variable is causing the syndrome early in the HLLES process. At least

in ocean surgeons, if you stop the experiment just when you start seeing

HLLES and you do not have any complicating issues, the lesions heal

fairly quickly so the euthanasia question should be need to be

performed.


M. Andrew Stamper D.V.M., Dipl. A.C.Z.M.


Research Biologist/Clinical Veterinarian


Disney's Animal Programs and Environmental Initiatives


Walt Disney World Resorts
 

Dogtown

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My new Ozotech Poseidon 200 ozone generator showed up at the door today from BRS. I should have it installed in a couple of days.

ozotechfile-1.jpeg
 

Dogtown

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I am using my royal Exclusiv skimmer since it's built/designed to support ozone use. I will however seal off all but one of the vents on the skimmer cap/top. The one remaining vent will be retrofitted to channel exhaust air through 3 feet of 1/2" silicone tubing over to 3/4" schedule 40 pvc. The pvc will route the exhaust outside the house.

I learned that standard silicone tubing is rated very safe for ozone use and pvc is rated safe.

Discharge water passes through activated carbon.

Randy Holmes Farley exhausts his own ozone in a similar fashion, which is where I got the idea.
 

shiftline

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I bolt a acrylic ring to hold carbon ontop of my skimmer vent holes

Do you think carbon is required ok the skimmer flow output when running a low amount? I have read many mixed opinions on this.

My plan is to run 25mg for about 3h a night on a 120g tank
 

Dogtown

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I bolt a acrylic ring to hold carbon ontop of my skimmer vent holes

Do you think carbon is required ok the skimmer flow output when running a low amount? I have read many mixed opinions on this.

My plan is to run 25mg for about 3h a night on a 120g tank

As others have commented, the ozone that these generators create is very easy to smell. I have noticed this today as its my first day testing it.

I like what you are planning by running ozone only at night. That's a plus for long term safety and I think I will do the same. I also like that you are planning to run it at a very low setting 25mg and only for about 3 hours a night. I would recommend using an old school outlet timer. There is no need to risk a having a controller or powerbar problem that causes your generator to run longer than planned.

You didn't mention if you have a Redox probe running or not? If you don't, I would recommend getting one with a controller so that you can monitor and set your controller to shut down the ozone generator if ORP ever exceeds a given 350 before your three hour cycle is treatment if finished. My ORP was 340 this morning before I started the ozone test and has risen to 355 in just a few hours. The water is already noticeably clearer too.

Ozone in the air varies widely depending on the pollution level in the area where you live. If you live in city with a frequent low scores on quality air index ratings, you may be breathing in air with higher ozone levels already. Hopefully not of course! Here is a news blurb about Ozone levels in my own city. We almost always have a nice ocean breeze and clear skies and was surprised to find my own city has this issue from time to time.

Ozone Levels Unhealthy Across Tampa Bay Area

TBO.com Staff
Published: May 1, 2008
Updated: June 1, 2013 at 08:00 AM
TAMPA - If the air seemed hard to breathe Wednesday, it wasn't your imagination. Levels of ozone, also known as smog, rose above the federal standard for healthy breathing across Tampa Bay. This morning, ozone levels remained elevated, but computer models forecast they would stay below the healthy air standard set by the U.S. Environmental Protection Commission, said Jerry Campbell, director of the Hillsborough County Environmental Protection Commission. Ozone is generated when organic chemical compounds combine with nitrogen oxide emissions in the presence of sunlight. Nitrogen oxide emissions come primarily from autos and power plants. When levels are high, vulnerable groups, such as the elderly, the very young and people with pre-existing breathing problems, should limit outdoor activities. Ozone levels reached 87 parts per billion at 4 p.m. Wednesday. The recently adopted federal standard is 75 parts per billion.

Campbell said the high ozone levels Wednesday resulted from a high-pressure system that kept clouds away. "When there are no clouds, you're not getting that vertical mixing (of the air)," Campbell said. "During the dry season, it traps the pollutants, and when it gets this warm it's an engine for ozone." Campbell said high smog levels were reported from Gainesville down to Sarasota County and east to Polk County.



Consider an ozone test kit like the one below to measure the ozone in your house before and after starting an ozone regimen. The kit is cheap and may take some of the mystery out of the picture.

Macherey-Nagel, 90736, Ozone Test Sticks, Box Of 12 Strips. Determination of ozo
MN OZONE test strips are designed for quick, convenient and reliable onsite ozone testing. The easy procedure yields accurate testing results within 10 minutes.

Ozone is a colourless toxic gas. It is irritating to eyes and mucous membranes and can cause respiratory complaints. With ozone concentrations increasing world-wide, especially in the summer time, ozone testing becomes more and more important.

An ozone content of 180 μg/m3 in the air is considered as critical value above which sensitive persons should avoid strong physical exertion. The ozone values published in the media only represent the ozone concentrations in the vicinity of the measuring stations. However, actual ozone values in other locations can deviate considerably from these published values due to meteorological and chemical influences. The reasons for such deviations are for wind, solar radiation, exhaust gases from vehicles etc. For this reason an on-site measurement of ozone concentrations is recommended.

Ozone testing is performed in a wide variety of settings and by multiple different users, such as schools and universities, sports teams, municipal authorities, and regular households. On site ozone testing is especially important prior to physical activity on sunny and hot days.

MN OZONE test strips are a perfectly suitable and convenient testing device for the orienting determination of ozone concentrations in air. Similar to the QUANTOFIX test strips they consists of plastic strips (10 mm wide) onto which a test paper has been sealed at the lower end. The strip design allows easy testing and handling.
 

Randy Holmes-Farley

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Randy - how much ozone #/mg to what size of system did you have the ozone on?

Ozone and the Reef Aquarium, Part 3: Changes in a Reef Aquarium upon Initiating Ozone by Randy Holmes-Farley - Reefkeeping.com
http://reefkeeping.com/issues/2006-05/rhf/index.php

Ozone was supplied by a 100 mg/hr Aqua Medic corona discharge ozone generator. In most cases, an Optima air pump sent the air through a Red Sea air dryer (500 g model) and then into the ozone generator. I also experimented with a Tetratec Deep Water air pump, with little difference noticed. The air/ozone mixture was then mixed with aquarium water in three different ways: a Coralife ozone reactor, my skimmer (ETS 800 Gemini), or a tubing reactor of my own design. The effluent air and water were passed over granular activated carbon (GAC) before being returned to the room and the aquarium, respectively (except when using the skimmer, where no GAC was employed).

My aquarium system consists of two main tanks (120 gallons and 90 gallons) and a variety of sump and support systems, including skimming, large macroalgae and sand-filled refugia. The aquaria contain a variety of fish, live rock, sand and invertebrates, including both hard and soft corals. In short, they are typical "mixed" reef aquaria. Near the end of this article is a section that details the nature of my aquarium system so that aquarists can understand whether their system deviates from mine in some important way(s).
 

Dogtown

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Randy, Aren't you still using ozone from time to time to clear up yellowing conditions in your water?
 

Randy Holmes-Farley

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I took down the tank a while ago, but what I did for a lengthy period after stopping the regular ozone use was every once in a while (less than once a month), trickle in a very small amount of ozone into my skimmer for 6-12 h. Not sure what effect it had, but less yellowing was the goal.
 

Dogtown

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@Randy, That must have been a big deal for you to tear down your tank after all these years. We all make adjustments to keep life headed in the right direction. For my own selfish reasons, I hope you start your own new build in the near future. I’m sure I’m not alone with that thought.

As far as the ozonator, Its been running for a couple of months now. It really does work very well and the water clarity is amazing. O2manyfish wasn’t kidding when he told me I’d see the difference.
 

TbyZ

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There are plenty of good reasons to use ozone. As well as a few bad ones. But the posistive outweigh the negatives. Ammonia oxidation is one good reason, so is increased dissolved organic removal by carbon.
whats the connection between increased carbon efficiency & ozone ?
 

scottbapilot

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Somthing weird is going on, I bought an enexpensive ozone generator to experment with. My ORP was 220 when I first checked it now its down to 175 while running the generator. Any ideals?
 

Dogtown

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Somthing weird is going on, I bought an enexpensive ozone generator to experment with. My ORP was 220 when I first checked it now its down to 175 while running the generator. Any ideals?
How long have you been running it?
 

Cory

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whats the connection between increased carbon efficiency & ozone ?

Sorry i just seen this. Im not sure what ozone does to organics but it makes carbon remove organics better.
 

Cory

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Somthing weird is going on, I bought an enexpensive ozone generator to experment with. My ORP was 220 when I first checked it now its down to 175 while running the generator. Any ideals?

The only thing i can think of is something died or you added a supplement that reduced orp. Or somethings buring inside the reactor or tank.
 

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