who's down with ORP?

jhale

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Bromine activation in the troposphere by the dark reaction of O3 with seawater ice. Oum, K. W.; Lakin, M. J.; Finlayson-Pitts, B. J. Department of Chemistry, University of California, Irvine, CA, USA. Geophys. Res. Lett. (1998), 25(21), 3923-3926.

Abstract:
There is increasing evidence that Br2 atoms play a role in tropospheric chem. in the marine boundary layer. In addn., they are believed to lead to rapid depletion of surface level O3 in the Arctic at polar sunrise. While mechanisms have been proposed for recycling Br2 atoms from sea salt particles, the initial reaction(s) leading to the formation of Br atom precursors is not known. Formation of gaseous Br2 from the reaction of seawater ice with O3 in the dark is reported. These observations suggested this reaction is a potential source of tropospheric photolyzable Br2 in high latitude coastal regions in winter. In addn., it may be the source of the photolyzable Br2 gas measured recently in the Arctic by G.A. Impey, et al. (1997), believed to be responsible for O3 destruction at polar sunrise.
 

jhale

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Evaluation of ozone disinfection from view points of inactivation disinfection effects and byproducts formation. Hatatatsu, Toshika; Suzuki, Yutaka. Advanced Wastewater Treatment Division, Public Works Research Institute, Ministry of Construction, Tsukuba, Ibaraki, Japan. WEFTEC 2000, Annu. Conf. Expo. Water Qual. Wastewater Treat., 73rd (2000), 4273-4287.

Abstract:
O3 has strong disinfecting power, but it might produce toxic byproducts, such as aldehydes and bromate ions. Inactivation effects and byproducts formation by O3 disinfection when O3 was used for wastewater disinfection were examd. There were few problems with residual O3 or ozonation byproducts and their toxicity, even if the inactivation level was as high as -4 log to -5 log coliform group survival ratio. Byproduct concns. increased and toxicity was higher when seawater was added. The presence of Br- is the key factor which causes O3 disinfection to form toxic byproducts.


Toxicity of ozonated sea water to Penaeus chinensis and Paralichthys olivaceus. Jiang, Guoliang; Liu, Yun; Yang, Dong; Lu, Yan. College of Marine Life Sciences, Ocean University of Qingdao, Tsingtao, Peop. Rep. China. Haiyang Kexue (2001), 25(3), 11-13.

Abstract:
The toxicity of ozonized sea water to the Penaeus chinensis and Paralichthys olivaceus was studied. The results showed that the tolerance of shrimp for residual ozone levels was much higher than that of the fish, the shrimp would live 48 h in ozone water ? 1mg/L, while fish could not live more than 3 h. Concn. lethal to 50% of sample fish of Bastard halibut for 48 h was 0.13 mg/L. Compared with other disinfecting method, the ozonation is a good treatment method for intensive aquaculture with suitable level.

Effect of seawater treated with ozone on content of protein, amino acid and carbohydrate in Chlorella sp. Wang, Chenggang; Tang, Xuexi; Zheng, Bo; Tang, Xiaohua. Shandong Marine Science and Technology Academy, Tsingtao, Peop. Rep. China. Haiyang Kexue (2001), 25(2), 15-17, 23.

Abstract:
The effects of seawater treated by ozone on contents of protein, amino acids, and carbohydrate were studied in Chlorella sp. at the different growth stages. The results showed as follows: a certain dosage of ozone treatment could increase the content of protein and amino acids, but decrease the content of carbohydrate. The proportion of necessary amino acids for fish to the total amino acids in the microalgae did not exhibit significant change compared with control group. Ozone treatment of Chlorella sp. could promote the whole nutrient level.

Effects of ozone-produced oxidants on ventilation of the pearl oyster, Pinctada fucata martensii. Yamamoto, Ken-Ichi; Kondo, Masakazu; Handa, Takeshi; Nakamura, Masatoshi. National Fisheries University, Shimonoseki, Yamaguchi, Japan. Suisan Zoshoku (2000), 48(3), 509-516.

Abstract:
To evaluate the effect of ozone-produced oxidants (OPO) on the ventilation of the pearl oyster, Pinctada fucata martensii, the ventilation vol. (Vg), the gill cilia movement (SP) and the surface structure of gills were examd. after exposure to ozonized seawater for 24 h. Vg was examd. every 3 h during exposure to the seawater of OPO 0.70 mg O3/L. Also the day when Vg recovered to the level of the control after exposure (DY) was examd. In the 24 h, Vg and SP decreased with an increase in the OPO concn., and showed zero at 0.58 mg O3/L or more. DY was under 23 days at 0.42 mg O3/L or below, and 10-80 days at 0.58-0.70 mg O3/L. However, at 0.58-0.70 mg O3/L, 20% of the individuals used for the expt. died 5-76 days later. Every 3 h, Vg decreased with time. DY was under 23 days within 12 h and 25-80 days at 24 h. The damages of the gills were postulated to progress in the order: the frontal cilia disappeared, the lateral cilia disappeared, the ciliary disk collapsed, and the gill filaments disappeared from the tip.

Analysis of residual ozone (in fresh water) or residual oxidants (in seawater) by spectrophotometry with DPD reagent. Anon. UK. Res. Discl. (2000), 438(Oct.), P1800-P1801.

A couple of good things for fish

Abstract:
Adaptation of a spectrophotometric method for the detn. of free chlorine in water to the detn. of O3 and other oxidants is described. The method uses N,N-diethyl-p-phenylenediamine in the presence of KI as the reagents. The detn. limit of the method is 0.014 mg O3/L.

Surface disinfection of Atlantic halibut Hippoglossus hippoglossus eggs with ozonated sea-water inactivates nodavirus and increases survival of the larvae. Grotmol S; Totland G K Department of Aquaculture, Institute of Marine Research, Bergen, Norway. sindre.grotmol@imr.no DISEASES OF AQUATIC ORGANISMS (2000 Jan 14), 39(2), 89-96.

Abstract:
Disinfection by ozonation of sea-water may reduce the risk of transmission of nodavirus, a major fish pathogen, via Atlantic halibut Hippoglossus hippoglossus eggs. In the present study, eggs at 4 d prior to hatching were exposed to nodavirus and then to ozonated sea-water using different concentrations (0.3 to 10 mg l-1) and exposure times (0.5 to 10 min). None of the larvae from virus-exposed eggs washed with ozonated sea-water developed viral encephalopathy and retinopathy (VER), which was detected in all dead larvae from eggs exposed to nodavirus but not washed with ozonated sea-water. In the non-treated control group about 20% of the dead larvae developed the disease. This suggests that the halibut eggs taken from a large-scale production facility were already contaminated with nodavirus. The egg groups which had been treated with 4 mg O3 l-1 for 0.5 min or with lower total ozone exposures had a higher survival and no adverse effects on the development of the larvae after hatching were observed. Although a slight delay in hatching was found, after 2 d the cumulative hatching had normalised. In the egg groups with high total exposure (4 mg O3 l-1 for 1 min or higher total ozone exposures) a pronounced negative effect on hatching was observed. Our results indicate that the egg surface may be important in the transfer of nodavirus and that nodavirus associated with the surface of the egg may be inactivated by ozonated sea-water.
 

jhale

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NYPDFrogman said:
OK let me ask this
can you have good water quality with a low redox potential?
or can you have poor water quality with a high redox potential?( I'm not talking extremes)

a more definative answer,

"is the water any cleaner?

No. And I do not subscribe to the often accepted idea that higher ORP means cleaner water. Adding high ORP materials to the water will raise ORP, but not make the water cleaner in any sense. Likewise, adding a little of an antioxidant (like vitamin C) to the water will make ORP plunge. Is the water a lot dirtier in that case?"

from this thread
 

jhale

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more info on ozone use from Boomer

Yes, ozone will produce nitrates. Ammonia gets oxidized to Nitrite and the nitrite to nitrate as it picks up another O from the ozone

NO2 + O3 ---> NO3 + O2

Schlesner, wrote a paper on this

Schlesner, Auswirkungen einer Seewasserreiningungsanlage mit Ozon, Thesis (The effects of seawater purification plant using ozone)


I also have some of his NO2--->-NO3 graphs, were it shows an increase in NO3 from NO2 with ozone from 90 ug NO2-N to 0 NO2-N from 10 to 180 min, while the NO3 increases from 375 ug NO3-N to 800 ug from 10 to 180 min.
.

Here is some more

Oxidation

Inorganics-
Oxidation of inorganics with ozone will not result in the removal of metals, but it does facilitate their precipitation and subsequent removal through filtration.

Iron and manganese are easily and readily oxidized into a particulate for filtration downstream.

Sulfides are rapidly oxidized to sulfates, thus eliminating the ?rotten egg? taste and odor associated with sulfides.

Heavy metals such as arsenic, copper, and lead are easily reduced to below detection limits with ozonation followed by filtration.

Trace metal removal of cadmium and zinc through oxidation with ozone and subsequent filtration has been found to be effective in reaching MCL levels established by the USEPA in the SDWA.

Nitrite ion is oxidized very quickly to nitrate as are organic nitriles, nitrites, nitrous compounds, hydroxylamines and the like.

Organics

The USEPA has identified over 700 individual organic compounds, many of which may be readily oxidized to carbon dioxide by ozone, while others are not affected at all. The use of ozone on organics is typically followed by filtration with granular activated carbon (GAC).

Advanced Oxidation Process (AOP) refers to increasing the reactivity of ozone in water. This is performed by forcing ozone to react via a free radical pathway. There are two methods commonly used to attain AOP:
1. Hydrogen Peroxide (O3 + H2O2)
2. Ultraviolet Radiation (O3 + UV)

Many molecules that are resistant to ozone alone are degraded by this free radical process. AOP utilized on organics that normally react to ozone will reduce the initial ozone dosage required by approximately 20%. AOP is used most often to control organics (taste, odor, color, THM precursors, micro pollutants and pesticides). This is not to say that AOP is required for oxidation of organics, but in some instances it may be preferred.

Trihalomethane (THM) precursors (humic and fulvic acids) are not formed until they are chlorinated. Therefore, it is best to control the THM precursors prior to chlorination (if required after ozonation) by partially oxidizing them with small amounts of ozone. Normally, the ozonated water is then passed through sand and/or GAC filtration. The partially oxidized THM precursors are biologically degraded in the sand and/or GAC filters.

Volatile Organic Contaminants (VOCs) may be reduced dramatically (up to 97%) by ozonation followed by GAC.

Synthetic Organic Contaminants (SOCs)/Micro pollutants - Ozone or AOP is capable of removing many SOCs. This removal leads to the transformation of these molecules into toxic or non-toxic by-products which are easily removed through subsequent GAC filtration.

Color derived from the decomposition of naturally occurring humic materials (organics) is easily removed with ozone followed by GAC filtration.

Pesticides such as phosolone and aldrin are oxidized to destruction.

Toxic Cyanide ions are readily oxidized by ozone to the much less toxic cyanate ion.

Turbidity/Microflocculation

Ozone, used as an aid to coagulation prior to the injection of chemicals, enhances the process through microflocculation and reduces chemical demand. Ozone should not be mistakenly applied as a replacement to the coagulation process, but as a superior coagulant aid.
 

jhale

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your the only one who cares D.

There is still more to discuss about ORP, the ozone topic took over the thread.
And I think our one scientist got frustrated and left :p

As there is apparently no article I could find that deals with ozone pertaining to the reef aquarium I'm going on peoples opinions and as you see above ozone studies geared towards the commercial fish market. I can't believe there has never been a study done for ozone in a reef tank. But if Randy can't find one either then I guess that's the case.

ORP and Ozone are linked in that you best have a ORP controller if your running ozone. But there are other things you can do to raise the ORP of your water besides just using ozone. The tricky part is understanding that a high ORP does not necessarily mean you have good water quality. This could be why Randy says he does not bother testing for it.

As for the Ozone I've found some more info, but i think i've posted enough for now, lol, I'd like to see what people have to say before I pile on more info.
 

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jhale said:
your the only one who cares D.

There is still more to discuss about ORP, the ozone topic took over the thread.
And I think our one scientist got frustrated and left :p

As there is apparently no article I could find that deals with ozone pertaining to the reef aquarium I'm going on peoples opinions and as you see above ozone studies geared towards the commercial fish market. I can't believe there has never been a study done for ozone in a reef tank. But if Randy can't find one either then I guess that's the case.

ORP and Ozone are linked in that you best have a ORP controller if your running ozone. But there are other things you can do to raise the ORP of your water besides just using ozone. The tricky part is understanding that a high ORP does not necessarily mean you have good water quality. This could be why Randy says he does not bother testing for it.

As for the Ozone I've found some more info, but i think i've posted enough for now, lol, I'd like to see what people have to say before I pile on more info.

the stuff you posted was great not the type of stuff you can just skim through.
like much of info shared in this hobby it's sometimes highly opinuated.
I wouldnt suggest that Ozone itself is the "Savior" or final word, or the missing element in a perfect reef tank enviorment. there is no subsituted for diligent care and husbandry ( I think I said that before) but I do think it's a helpful tool.
the problem is that most, including myself read and retain what we feel is important or the answer we are seeking, and ignore the rest.

there are many arguements for and against Ozone. we kind of strayed from the original topic regarding ORP but it went in a good direction because Ozone is related to ORP and to an extent ORP is related to water quality.
Ideally it would be nice to be able to measure everyones ORP and see what is really occuring, different filtration, skimmers, etc.
 

jhale

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I agree Frank, thanks for posting to by the way :)

At the moment I'm leaning towards using ozone in a limited fashion, I guess the way Pierce is using it, to clear the water once in a while.
Since there is no definitive report that tells us if ozone is making the water healthier for the coral and fish I can't say I would feel comfortable running it 24/7.
We know it definitely is not healthy for any plankton or free swimming coral larvae in the tank, you can kiss them goodbye.
And what spykes posted is interesting, but still not proven either way. I would think if O3 was changing the trace elements that corals use to a form they could not use that anyone who used ozone would have reported corals dying left and right in their tanks, but that's not the case.

The other main concern is what ozone will do to your skimmer production as time goes by. The majority of people reporting on skimming and ozone have been running the ozone directly through the skimmer. This will obviously have a direct effect on the skimmate produced as you are oxidizing the organic material as it enters the skimmer, how could the production not be effected.
I think that running the ozone in it's own reactor, and after the skimmer is the way to use it. You give the skimmer it's chance to remove the organics, and the ozone reactor can then clean what the skimmer did not take out.
I know we keep saying the same things over once in a while, but my understanding of ozone and ORP is changing slowly since I have to read through tons of posts to find helpful material, and the occasional article.
 

jhale

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for those interested new information will be published soon.

I asked our own hermangareis to get in touch with his father in germany, who happens to be a scientist and is an expert in the care of reef tanks. he has responded with something herman is now translating :) what ever his opinion it should be interesting.

Also Frank and I spoke about ORP and ozone at the holiday party. He will have ozone on his tank in the next week or so and will keep track of the water quality as he uses it.

One thing I am concerned about is the linkia multiflora I just got. It only eats micro-organisms off the rocks. I'm thinking ozone may not be so friendly to this food source if they depend on the water column to find each other and reproduce.
 

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Looking through this thread I honestly think that you guys are disecting it a little too much leading to a bit of confusion. Looking through it seems that a lot of the tests conducted are effects of ozone on the aquarium inhabitants, when in actuality it should not have any effect on fish or corals etc since there should be absolutely no exposure to the above mentioned inhabitants. O3 should also not affect "lesser organisms living in the rock/sandbed since once again there is no exposure.

Ozone is not something that we dose like trace elements into the tank that will flow through our entire system. It is a separate system that is linked to the tank, and if used correctly will not leach into the main system. O3 will only treat the water that flows into the reactor and nothing else.

When using ozone it is never used as a constant like the protein skimmer or a pump. It is something that is used in conjuction with a controller, whether it be an electronic controller or a manual controller (pierce).

The fact is that O3 is such a complex topic that I can say with certainty that not a singe member understands fully or they would be working in a different field.

I also read that people have been "scared" off this thread - I dont believe that people got scared away but more that they got bored with the "ununderstandable & way to complex regurgitations". I am not trying to offend anyone in any way because when it comes to understanding biochemistry I am sure that there are plenty of people that are far more proficcient that I am.

The only thing I am trying to say is, keep the O3 discussions to the actual practical aspect of reefkeeping.

Like Frank said. Using O3 is good on some tanks and detrimental on others. People that are avid Zeolith followers will never advocate the use of O3 because it counteracts the elements dosed into the system.

It would therefore be more beneficial to the readers of this thread if we kept the thread more practical....

Just my 2 cents
 

jhale

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here's the thing that's being debated, not whether the ozone will hurt the fish, but if killing everything in the water column will have a detrimental effect on the coral and fish.

there is very little written on the subject. what is out there is technical.
this thread is a precursor to topics that will be covered in the upcoming advanced reefing forum. I'm not saying I understand everything I posted, but I think we should do our own research. so I'm still studying. and like I said before Franks going to be the ozone guinea pig.

ORP is a difficult subject for chemists to understand, and ozone is a highly debatable issue. I don't think you can get too technical for either. I'll admit this type of thread is not going to be for everyone, and if they are bored no one is making them read all the junk that's here. you can just wait till the conclusions are drawn, i.e. skip to the end ;)
 

kimoyo

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jhale said:
there is very little written on the subject. what is out there is technical. this thread is a precursor to topics that will be covered in the upcoming advanced reefing forum. I'm not saying I understand everything I posted, but I think we should do our own research. so I'm still studying. and like I said before Franks going to be the ozone guinea pig.
This added to companies trying to sell expensive ozone equipment to hobbyist is a big problem.
 

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I've been surfing trying to find info also. most stuff I've found is very technical and the stuff I've found thats reef related is subjective to say the least.

untill now I was under the impression that orp was directly related to water quality in the sense that a higher ORP meant better water quality.
I must admit I'm very confused.
my tank is doing well good coral growth, no nusicance alage, Zero phosphates, zero nitrates, my water is crystal clear.


my skimmer seems to be doing a very good job, I do a 25% water change monthly. my ORP at it's highest is 380 with a skimmer, filter socks and a carbon reactor. i was hoping Ozone would give me the "edge" in coral growth and color and help deal with my large fish population.

during my reading I found out that the addition of O2 can also raise ORP.
Ther is no optimium value for a reef tank. in a natural reef ORP values range from 350-450mv

Solby questioned the need to sterlize the water column
I got this from an article written by Randy Holmes-Farley
Simplified ORP

Imagine a reef aquarium as a vast battlefield. No, more vast. Much, much more. OK, that's ORP. That is, ORP is a measure of who is winning and who is losing the battle. The battle is never won by one side or the other. As an aquarist, you do not want it to be, or else everything in the tank would be dead. In other situations, such as the purification of tap water for drinking, allowing the oxidizers to win is fine. A high enough ORP (650+ mv) can kill most bacteria in a few seconds.


if you'd like to read the complete article here's the link
http://www.reefkeeping.com/issues/2003-12/rhf/feature/index.php

I'm going to set up my Ozone later this week I'm waiting for a check valve and my dissolved 02 test kit.

I plan to set my controller at 400mv to start and see the result and eventually to 450mv
I'm have a feeling that my Ozone will not run that often to reach these levels
and when it's not the reactor will simply be an o2 reactor keeping the water saturated. it's going to be interesting to see the results.
 

Deanos

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NYPDFrogman said:
my tank is doing well good coral growth, no nusicance alage, Zero phosphates, zero nitrates, my water is crystal clear.

NYPDFrogman said:
i was hoping Ozone would give me the "edge" in coral growth and color and help deal with my large fish population.

Can you go into more detail about what you expect from Ozone? :scratchch The "edge" reads a little vague :confused:, especially when discussing coral growth measured in millimeters monthly.

Wouldn't zero nitrates and phosphates hint that your fish population isn't overwhelming your current filtration? Your water is crystal clear and you seem happy with your coral growth and skimmer production. The grass isn't always greener...
 

jhale

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Deanos said:
Can you go into more detail about what you expect from Ozone? :scratchch The "edge" reads a little vague :confused:, especially when discussing coral growth measured in millimeters monthly.

my edge includes super clear water that lets more light get to the coral.
 

ShaunW

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NYPDFrogman said:
Solby questioned the need to sterlize the water column
I got this from an article written by Randy Holmes-Farley
Simplified ORP

Imagine a reef aquarium as a vast battlefield. No, more vast. Much, much more. OK, that's ORP. That is, ORP is a measure of who is winning and who is losing the battle. The battle is never won by one side or the other. As an aquarist, you do not want it to be, or else everything in the tank would be dead. In other situations, such as the purification of tap water for drinking, allowing the oxidizers to win is fine. A high enough ORP (650+ mv) can kill most bacteria in a few seconds.


if you'd like to read the complete article here's the link
http://www.reefkeeping.com/issues/2003-12/rhf/feature/index.php
This is such a ridiculous statement in so many ways, I don't even know where to begin. Some experts should stick to their speciality.
 
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