Copper in Water

[JamesG161]

I found this is a better place to talk about stuff that was part of this post...
http://forums.sailboatowners.com/index.php?threads/copper-free-bottom-paint.181396/#post-1324436

This is the most informative and factual spot to read about it...
https://en.wikipedia.org/wiki/Anti-fouling_paint

Here is the proposed EPA standard...
https://www.federalregister.gov/doc...nt-estuarinemarine-water-quality-criteria-for

And for you WA state folks...
http://unicorn.ps.uci.edu/M3LC/handouts/Seawater.pdf
is Pacific Water. Please note that Zinc, that we use to prevent loss of Iron, is at around the same concentration in Pacific waters.

This proposed concentration is < 1 gram Cu in a Million grams of Water. < 1 ppm.
Copper free in water is normally in the form of Copper Carbonate (CuCO3)
Which mean Copper takes up CO2 from the atmosphere ( a good thing) or chemistry
2 Copper takes up 3 (CO2) from the air.
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The copper in antifouling paints...
Here is a quote from the Wiki...
Washington State has passed a law which may phase in a ban on copper antifouling coatings on recreational vessels beginning in January 2018.[11] However, a similar ban was rescinded in the Netherlands after the European Union's Scientific Committee on Health and Environmental Risks concluded The Hague had insufficiently justified the law. In an expert opinion, the committee concluded the Netherlands government's explanation "does not provide sufficient sound scientific evidence to show that the use of copper-based antifouling paints in leisure boats presents significant environmental risk"
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From SPURIOUS information, some bored people decided to SAVE the Salmon.

Then they need to replace all Copper water piping in all of the homes whose sewage treatment waters flow to the ocean. This is the largest source of Copper is for antifouling of drinking water.

One Active Volcano puts more Copper in the ocean in one minute, than all of the Copper from all of the bottom paints ever made. I have 2 friend who say the fishing in Hawaii is great!!
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This intended as Myth Buster. I am totally surprised and will now add my scientific opinion to the EPA new ruling.
Jim...

 

[Don S/V ILLusion]

As a chem. engineer and environmental scientist with more than 30 years of professional experience in env. science, I can assure you copper is toxic, even in small concentrations, to lots of marine critters,

From a common sense perspective, if copper was not toxic, it wouldn't be an effective anti-fouling.

 

[SFS]

As a chemist and an environmental scientist with more than 30 years of professional experience in environmental consulting and chemical analysis, I can confirm that Don is absolutely correct. Copper is toxic, even in very small concentrations, to lots of marine species.

 

[CloudDiver]

This about the 80th time I need the 'face palm' emoticon but they just don't have one...
@JamesG161 wasn't making the argument that copper isn't toxic to the marine environment, he's talking about the amount of copper being contributed to the oceans by the use of anti-foul paints on leisure craft... which is .00000000000000001 percent of what ends up in the ocean after a volcanic eruption. Or better yet, .00000000000001 percent of what the commercial marine industry and other industries put in the water every year.
Since we all have to whip out and measure our 'stuff'... After several years as a Naval Officer I always saw the bottom of my Destroyer anti-fouled in dry-dock at least once during my tour on two ships. Formulas may have changed since then but I can promise you that in 2003 you can be darn skippy that there was still copper in the International paint we used at that time. The number of gallons used on a 505 ft Destroyer was probably enough to bottom paint every single leisure sailboat privately owned in the entire county of San Diego. Now multiply that by every ship is the US fleet.

Point is gentlemen, its not about what is 'poisonous' and what is not, its about what leisure vessels contribute to the pollution vs. what the commercial industry, other heavy industry pollution, and acts of nature do. This crap has been going on for last 15 or so years with off-road racing and motorcycles in general. CARB and the EPA try to come down on leisure vehicles because they are an easy target, while commercial trucks spew out more pollution in a single day than every single motorcycle in the country does (even 2 strokes) in an entire year.
Its not about science, its about politics!
Don't even get me started on the dozen or so commercial oil tankers out there still burning bunkers.... sheesh.

 

[Don S/V ILLusion]

Please don't confuse wide-area contamination from STPs or other sources with this. I thought the subject was the toxicity of ant-fouling copper containing paint. You can dismiss it by rationalizing bigger issues but that changes nothing.

Dead zone are ubiquitous in marinas largely because of copper paint leaching.

 

[JohnVTX]

 

[fstbttms]

Most of you are missing the point. The point is that the places where pleasure craft congregate (marinas, mooring fields etc.) tend to be enclosed and receive relatively poor tidal flushing. Further, the great majority of the pleasure craft in these marinas (each and every one pumping copper into the environment every single second they are in the water) move infrequently, if at all. The copper their anti fouling paints leach into the water column therefore impacts a relatively localized area and does so pretty significantly. The USEPA decades ago set water quality standards for heavy metals like copper. And frequently, in the places where pleasure craft congregate, these standards are being exceeded for copper. Studies have shown that copper-based anti fouling paint is the major contributor, through both passive leaching and yes, even in-water hull cleaning.

Arguments about commercial and naval ships contributing more are invalid, as these vessels do not follow the same use patterns as pleasure craft, are regulated differently than pleasure craft and in any event, spend most of their time at sea where copper loading is not a concern.

 

[fstbttms]

I found this is a better place to talk about stuff that was part of this post...
Here is the proposed EPA standard...
https://www.federalregister.gov/doc...nt-estuarinemarine-water-quality-criteria-for

While this document was an excellent find and one I was unaware of, it is not a proposed standard for copper in the water (if that's what you meant.) The document actually announces the availability of a new criteria for measuring the bio-availability of copper to marine organisms. The biotic ligand model (BLM) may actually show that copper is not as much of a problem as previous methodologies have indicated it is. This would be a good thing for fans of copper-based anti fouling paint, of which I am one.

 

[JamesG161]

Most of you are missing the point. The point is that the places where pleasure craft congregate (marinas, mooring fields etc.) tend to be enclosed and receive relatively poor tidal flushing.

Now that is a key point!!!

Dilution is the solution to Pollution!

In fact, toxicity levels are measured by CONCENTRATION and EXPOSURE TIME!

Since we are pulling out the credentials, Master of Science Chemical Engineer, minors in Chemistry and Math. 30 years as Research (include Environmental) and Construction Engineering. Ran all Environmental Control Areas in the largest production department for the Largest Chemical Company in the World. Negotiated 4 - Region 4 EPA plant permits. And more.... I also claim Environmental scientist!

Of course Copper is toxic at levels of 1.3 PPM and contained 4 Day exposure (run salmon run and don't kiss the bottom of a copper painted boat) if you read the EPA background toxicity data, I linked. That is why it works.
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Now all you chemical guys... just where is the concentration toxic enough to kill algae, slime, barnacles, and other "cling on" sea life? By the way, the Bollards I tie to, are full of slime and barnacles just 2 feet away from my Petite SR bottom paint. Diver just looked and videoed my 43' boat bottom and smiled "I don't have to clean the bottom, again" and my AC stainer was so packed the Algae it too pliers to pull it out. The copper toxicity is when when barnacle begin they "isolate and contain" ( just like @fstbttms remarked) and thus THEY concentrate the toxicity. Same is true for Algae. My marina canal is basically purged but tidal changes and rain fall. I can cast net shrimp from the bow of my berthed boat.

If you look at the WA state link, they recommended using BORAX to clean your bottom. Guess what, someone else went GA GAH's when I suggested that Boron is nature anti fungus and mildew killer. Boron, Zinc , Chromium in your Stainless Steel shaft, and many more metal ions are toxic at high enough concentration. Check out the toxic metals in your Vitamin and Mineral supplements.

not a proposed standard for copper

But that is the standard that WA state references for the reason for making their, single state, law.
@fstbttms you nailed it! CONCENTRATION!
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Copper is NOT a free ion in fresh/ocean waters, it combines readily with dissolved CO2 to make a low toxicity CuCO3. So does every mollusk etc. Using CO2 from air and the photosynthesis cycle. So no CO2 then, ooopsss it becomes toxic to the life that clings to the bottoms, where concentrations and exposure time is prevalent.
https://en.wikipedia.org/wiki/Copper(II)_carbonate

But YOU drink free Copper ions (not combined) in every common public water fountain along with Toxic free Chlorine.
BTW DON'T TOUCH the Statute of Liberty and fish near there from toxic Copper.
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@Don S/V ILLusion and @SFS I have respected your knowledge in chemical discussions in SBO posts, so I don't mean to cast dispersions on your valid comments.
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Jim...

PS: LOL, this is NOT the war room.

PSS: @CloudDiver this is my face palm combo and maybe add this .

 

[justsomeguy]

Dilution is the solution to Pollution!

No, it isn't.

 

[CloudDiver]

I'm just really sick of the arguments... Not that anyone's opinions are not valid and I believe we all respect and want to preserve the Ocean. But really, I can't take too much of this banter between us recreational mariners when I see Corporations and Industry get away with RAMPANT MURDER compared to what we contribute to the problem. 'They' have money & influence... collectively, 'we' do not.

 

[JamesG161]

No, it isn't.

oh yes it is and I win.

I will modify that a bit.....
Dilution is the Solution to meeting Governmental Regulations on Pollution Control.

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Even is science it is... but I will only suggest the science to confirm...
1) First and Second Law of Thermodynamics
2) The overall transport phenomena differntial equation.

@justsomeguy I would love to have a few beers and talk this over. Probably won't convince you but we would have a good time.
Jim...

 

[JamesG161]

I believe we all respect and want to preserve the Ocean.

Amen brother!

But we need reality checks from time to time to see what the real concerns of our oceans are. BTW the USA oceans that touch us we are pristine compared to the rest of the world. Our stuff in are NOT the problem.
Jim...

 

[Don S/V ILLusion]

oh yes it is and I win.

I will modify that a bit.....
Dilution is the Solution to meeting Governmental Regulations on Pollution Control.

________
Even is science it is... but I will only suggest the science to confirm...
1) First and Second Law of Thermodynamics
2) The overall transport phenomena differntial equation.

@justsomeguy I would love to have a few beers and talk this over. Probably won't convince you but we would have a good time.
Jim...

That's not science. Rather, it's a rationalization by virtue of the impracticability of applying point source controls. The part about thermodynamics is nonsense in the same context and when you base your argument on acute toxicity levels or LD50 levels in the absence of any consideration of the persistent effects, your "dilution is the solution" theme falls apart.

The moral of this story is that regulating anti fouling copper paint is based on sound science but most boaters resent it feeling persecuted because they perceive industrial pollution is a bigger problem.

 

[MarkZ]

I cannot contribute to the scientific argument, but I can offer this observation: Earlier this summer I made a video of carp, and a couple other species of fish, feeding on the bottom of my boat. They were making so much noise, day and night, that on many occasions I couldn't sleep. This time of year, on most evening I can see dozens of carp lingering near the surface around my boat. So far I have found zero (0) dead fish floating in our small bay. The turtle population is very dense also, and I haven't noticed any dead ones.

 

[fstbttms]

I cannot contribute to the scientific argument, but I can offer this observation: Earlier this summer I made a video of carp, and a couple other species of fish, feeding on the bottom of my boat. They were making so much noise, day and night, that on many occasions I couldn't sleep. This time of year, on most evening I can see dozens of carp lingering near the surface around my boat. So far I have found zero (0) dead fish floating in our small bay. The turtle population is very dense also, and I haven't noticed any dead ones.

So your point is what? That the copper leaching from anti fouling paint doesn't cause any harm to the environment?

 

[thinwater]

This proposed concentration is < 1 gram Cu in a Million grams of Water. < 1 ppm.
Copper free in water is normally in the form of Copper Carbonate (CuCO3)
Which mean Copper takes up CO2 from the atmosphere ( a good thing) or chemistry
2 Copper takes up 3 (CO2) from the air.

Are you sure this isn't 1-2 ppb? That is the value is see in the EPA fact sheet. I'm also certain from lab experience that 1ppm Cu would kill everything marine; the regulatory limit would logically have to be 100-1000 times lower.

From EPA Fact Sheet
Chronic (4-day average)
dissolved Cu 1.3μg/L

This 1000x error affects a lot of your reasoning. For example, copper carbonate is fully soluble in water at that level. If not, underwater running gear would have a stable green patina, which we know it does not.

----

However, I'm sympathetic to the idea that the copper thing is overblown. It is a required nutrient and I have seen no argument that diluted 10-100x lower it has any practical or theoretical potential for harm. Not all pollutants are like this. Lead, arsenic, and chrome 6 are always bad, with no lower limit. So while I can see that some marinas and heavy bottom cleaning practices could cause a small dead zone, I'm not sure this contributes to an area problem even 50' away. It seems logical if you are looking for a boogieman, but I'm not sure it is. This is a pollutant that responds to dilution.

The BLM is interesting. The documents make it clear why the muddy waters of the east coast have no problem; relatively large volumes of colloidal clays and higher TOC precipitate and deactivate. This should make sense to all water treatment guys.

 

[JamesG161]

Are you sure this isn't 1-2 ppb

You are right! I typed it wrong (at the time). I did double check my math on my calculator and got 1E-09. I saw in Pacific water nano moles. If my science was PPM, I would not have made this post.
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I found no reference to bio-accumulation.
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My reasoning is simple math and I not rationalizing something measured by MAN, proposed by MAN and described by MAN.
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Last time on my point. People over regulate the wrong things is a quest to do SOMETHING noble and usually based on the moral high ground.
Jim...

PS: Carp are algae eaters. Thanks all for the healthy discussion without someone saying I highjacked the thread.

PSS: https://en.wikipedia.org/wiki/Thermodynamics

 

[JamesG161]

I forgot...
PSSS: https://en.wikipedia.org/wiki/Transport_phenomena

 

[MarkZ]

So your point is what? That the copper leaching from anti fouling paint doesn't cause any harm to the environment?

It's just an observation. With several hundred boats in a small area, many or most painted with Petit SR, and fish eating from the bottom of boats seems like it would be a very toxic habitat. If the situation is as toxic as I'm being lead to believe, then it seems like I would occasionally see a dead animal.