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Restoring Alkalinity to the Ocean



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RE: organic alkalinity and iron nutrition17-05-2023 09:19
Im a BM
★★★☆☆
(595)
IBdaMann wrote:
Im a BM wrote:[quote]IBdaMann wrote:Would you define acidity as "alkaline neutralizing capacity"?
No trained scientist would call ANYTHING "alkaline neutralizing capacity"

What if, perchance, one is found?


Environ. Sci. Technol.1990,24,1486-1489
Acid Neutralizing Capacity, Alkalinity, and Acid-Base Status of Natural Waters Containing Organic Acids

Harold F. Hemond
Water Resources and Environmental Engineering, Department of Civil Engineering, and Massachusetts Institute of Technology Energy Laboratory, Cambridge, Massachusetts 02139

Downloaded by MIT on October 2, 2009 [url]http://pubs.acs.orgPublicationDate
ctober1,1990|doi:10.1021/es00080a005[/url]

The terms acid neutralizing capacity (ANC) and alkalinity (Alk) are extensively employed in the characterization of natural waters, including soft circumneutral oracidic waters. However, in the presence of organic acids, ANC measurements are inconsistent with many conceptual definitions of ANC or Alk and do not provide an adequate characterization of the acid-base chemistry of water.


------------------------------------------------------------------------------

This paper does not call anything "alkaline neutralizing capacity".

It DOES give good background on "The terms acid neutralizing capacity (ANC) and alkalinity (Alk)..." Recommended reading for those who have difficulty with these definitions.

But what is special about the paper is recognition that organic alkalinity is a not a negligible contributor to total alkalinity. Indeed, our understanding of alkalinity is incomplete without it.

Historically, the only measurement done was total alkalinity. Without knowing which anions were responsible, it was a simple titration with acid to reach a designated endpoint pH.

Later, it was recognized that there was value in more complete characterization of the species involved. Four categories of alkalinity were reported.
total alkalinity - indiscriminate measure of all acid neutralizing anions.
hydroxide alkalinity - that portion of total alkalinity supplied by hydroxide ions. Usually a tiny, tiny fraction of the total.
bicarbonate alkalinity - the lion's share of total alkalinity in most waters, supplied by bicarbonate ions.
carbonate alkalinity - the much smaller fraction of total alkalinity supplied by carbonate ions.

While it was known that other anions, such as phosphate, contributed to alkalinity, they were usually such a small fraction of the total, they were dismissed as negligible.

This paper points out that anions of organic acids should not be ignored.

Example: acetic acid (vinegar) has a pKa of about 4.75. This means that if a solution of acetic acid is adjusted to pH 4.75, exactly half of it will be dissociated into hydrogen ions and citrate ions. The other half remains undissociated citric acid - proton remaining attached rather than free in solution.

In contrast, hydrochloric acid has a pKa of -6.3
This means that the pH would have to somehow be driven down to -6.3 in order to get half the hydrogen ions to reattach to chloride and form intact hydrochloric acid.

To create pH below zero is possible, but almost never occurs in nature.

Chloride ions provide no alkalinity because they won't neutralize any acid until the pH is well below zero.

Acetic acid and its associated acetate ions, on the other hand, can be used to neutralize acidity at near neutral pH. Acetate buffers are used in chemistry.

So, it turns out that anions of organic acids are a much more important contributor to alkalinity than previously believed.

And they can do something very special that few other anions can.

Many organic acid anions can form strong complexes with iron - either in ferric iron(III) or ferrous iron(II) form.

Iron is a limiting nutrient in sea water.

Organic alkalinity is responsible for making iron available to support photosynthesis in the sea.
17-05-2023 10:04
IBdaMannProfile picture★★★★★
(14321)
Im a BM wrote:Acid Neutralizing Capacity, Alkalinity, and Acid-Base Status of Natural Waters Containing Organic Acids

I started reading through this but I had to stop. I'll get back to it later today. In the meantime, I was hoping you would explain something that is giving me a bad taste about this article. What does the author mean by "organic." The article uses the word "organic" more liberally than products at Walmart. As you know, carbon is an element and can't be organic, yet you have used the term, as does this article "organic carbon" like that is supposed to mean something important, just not important enough to explain it to those reading the article. Then it uses the term "organic acids" without explaining. At Costco they sell "organic" chocolate milk without explaining that either. Should I be ignoring this article or is there really something I, as the reader, need to know that the stupid author was too brain-dead to mention?

How am I, as the reader, expected to understand the word "organic" in this article? I know of many meanings, but the one that I would expect from a chemist is "carbon-based" or "of life/living/alive" ... and not this silly, seemingly redundant "organic carbon" crap. Anyway, I wouldn't care one way or the other if the author would explain up front instead of presuming that his readers are all mind-readers.

Im a BM wrote:The terms acid neutralizing capacity (ANC) and alkalinity (Alk) are extensively employed in the characterization of natural waters, including soft circumneutral oracidic waters.

I'm looking forward to reading all about it. Will the author be explaining these terms or am I expected to wonder what kind of waters are synthetic waters? ... and whether or not there are oralkaline waters and what that even means? Will the paper also discuss circumacidic waters and circumbasic waters ... or only the circumneutral waters?

Im a BM wrote:It DOES give good background on "The terms acid neutralizing capacity (ANC) and alkalinity (Alk)..." Recommended reading for those who have difficulty with these definitions.

I'm looking forward to reading all about it.

Im a BM wrote:But what is special about the paper is recognition that organic alkalinity is a not a negligible contributor to total alkalinity. Indeed, our understanding of alkalinity is incomplete without it.

What do chemists consider "substantive" in this case?

Im a BM wrote:Organic alkalinity is responsible for making iron available to support photosynthesis in the sea.

Seawater gets its iron from other sources; the alkalinity is incidental. Thermal vents, erosion, dust, etc. all bring iron into the ocean.
17-05-2023 16:58
IBdaMannProfile picture★★★★★
(14321)
Im a BM wrote:
Environ. Sci. Technol.1990,24,1486-1489
Acid Neutralizing Capacity, Alkalinity, and Acid-Base Status of Natural Waters Containing Organic Acids
Harold F. Hemond
Water Resources and Environmental Engineering, Department of Civil Engineering, and Massachusetts Institute of Technology Energy Laboratory, Cambridge, Massachusetts 02139

One small thing that bothers me about this paper is the unclear way CO2 is addressed. The author clears space on the page to clearly bilboard this:

TECHNICAL NOTE: Alkalinity and ANC are independent
of exchange with carbon dioxide and other atmospheric
gases. However, atmospheric gas exchange can alter concentrations of individual species, such as bicarbonate. Also,
aeration of a sample during filtration can cause mineral
precipitation on the filter—this alters alkalinity, especially
in water systems closed to the atmosphere under ambient
conditions.


First, it is erroneous to state that alkalinity is independent of CO2 exchange and then immediately state the direct impact of CO2 exchange. The word "however" is not a license to completely contradict what was just written in the preceding sentence.

Second, this note was a perfect opportunity to clarify that CO2 exchange is a cycle, i.e. it enters and it leaves, and that alkalinity is reduced somewhat when it enters, and that alkalinity returns to what it was when CO2 leaves. As it stands, it does nothing to correct the prevalent misconceptions that exist on this point. If evaporation exceeds precipitation, alkalinity results in an increase. If precipitation exceeds evaporation, alkalinity decreases. This is the paragraph that should have been the "Technical Note." As it stands, what was written essentially says nothing and only serves to fill space.

This is just one point. I still haven't finished reading the paper. I'll provide more commentary when I'm finished.
RE: Erratum, iron, and "alkaline neutralizing capacity"18-05-2023 08:19
Im a BM
★★★☆☆
(595)
Im a BM wrote:
IBdaMann wrote:
Im a BM wrote:[quote]IBdaMann wrote:Would you define acidity as "alkaline neutralizing capacity"?
No trained scientist would call ANYTHING "alkaline neutralizing capacity"

What if, perchance, one is found?


Environ. Sci. Technol.1990,24,1486-1489
Acid Neutralizing Capacity, Alkalinity, and Acid-Base Status of Natural Waters Containing Organic Acids

Harold F. Hemond
Water Resources and Environmental Engineering, Department of Civil Engineering, and Massachusetts Institute of Technology Energy Laboratory, Cambridge, Massachusetts 02139

Downloaded by MIT on October 2, 2009 [url]http://pubs.acs.orgPublicationDate
ctober1,1990|doi:10.1021/es00080a005[/url]

The terms acid neutralizing capacity (ANC) and alkalinity (Alk) are extensively employed in the characterization of natural waters, including soft circumneutral oracidic waters. However, in the presence of organic acids, ANC measurements are inconsistent with many conceptual definitions of ANC or Alk and do not provide an adequate characterization of the acid-base chemistry of water.


------------------------------------------------------------------------------

This paper does not call anything "alkaline neutralizing capacity".

It DOES give good background on "The terms acid neutralizing capacity (ANC) and alkalinity (Alk)..." Recommended reading for those who have difficulty with these definitions.

But what is special about the paper is recognition that organic alkalinity is a not a negligible contributor to total alkalinity. Indeed, our understanding of alkalinity is incomplete without it.

Historically, the only measurement done was total alkalinity. Without knowing which anions were responsible, it was a simple titration with acid to reach a designated endpoint pH.

Later, it was recognized that there was value in more complete characterization of the species involved. Four categories of alkalinity were reported.
total alkalinity - indiscriminate measure of all acid neutralizing anions.
hydroxide alkalinity - that portion of total alkalinity supplied by hydroxide ions. Usually a tiny, tiny fraction of the total.
bicarbonate alkalinity - the lion's share of total alkalinity in most waters, supplied by bicarbonate ions.
carbonate alkalinity - the much smaller fraction of total alkalinity supplied by carbonate ions.

While it was known that other anions, such as phosphate, contributed to alkalinity, they were usually such a small fraction of the total, they were dismissed as negligible.

This paper points out that anions of organic acids should not be ignored.

Example: acetic acid (vinegar) has a pKa of about 4.75. This means that if a solution of acetic acid is adjusted to pH 4.75, exactly half of it will be dissociated into hydrogen ions and citrate ions. The other half remains undissociated citric acid - proton remaining attached rather than free in solution.

In contrast, hydrochloric acid has a pKa of -6.3
This means that the pH would have to somehow be driven down to -6.3 in order to get half the hydrogen ions to reattach to chloride and form intact hydrochloric acid.

To create pH below zero is possible, but almost never occurs in nature.

Chloride ions provide no alkalinity because they won't neutralize any acid until the pH is well below zero.

Acetic acid and its associated acetate ions, on the other hand, can be used to neutralize acidity at near neutral pH. Acetate buffers are used in chemistry.

So, it turns out that anions of organic acids are a much more important contributor to alkalinity than previously believed.

And they can do something very special that few other anions can.

Many organic acid anions can form strong complexes with iron - either in ferric iron(III) or ferrous iron(II) form.

Iron is a limiting nutrient in sea water.

Organic alkalinity is responsible for making iron available to support photosynthesis in the sea.


-------------------------------------------------------------------------------

1. Erratum

The above post mistakenly (dyslexically) says "citric acid" and "citrate" in a couple of places where it should say "acetic acid" and "acetate".

Acetate buffer with low pH and high alkalinity.

Sea water has from about 0.002 - 0.0025 moles/liter alkalinity

An acetate buffer made from 2 molar acetic acid, adjusted to pH 4.75 with sodium hydroxide, will contain 1 mole per liter acetic acid and 1 mole per liter sodium acetate. The acetate anion provides 1 mole per liter alkalinity.

A pH 4.75 acetate buffer can have 500 times as much alkalinity as sea water.
Low pH does not necessarily mean low alkalinity.



2. Iron, iron everywhere, and not a drop to drink.

Iron is one of the most abundant elements found in sea floor sediments.

Iron is one of the most scarce elements found in sea water.

Nearly all the iron entering the sea comes in as solid particulates of ferric iron clay minerals. They are insoluble at sea water pH. Sink to the bottom and stay there.

Some of the iron entering sea water is in dissolved form.

Nearly all of it precipitates out into insoluble form.

Dissolved ferric iron immediately drops out to form insoluble ferric hydroxides.

Dissolved ferrous iron can remain soluble at sea water pH.

But it is readily oxidized in the presence of free oxygen by bacteria to form insoluble ferric iron.

Pretty much the only iron that can stay dissolved in sea water is bound to organic anions in chelation complexes. Literally, 99% of dissolved iron in sea water is complexed by organic anions.

Ferrous iron cannot be oxidized to ferric iron with its reactive sites occluded by organic ligands.

Ferric iron cannot form precipitates with hydroxide when its reactive sites are occluded by organic ligands.

And it turns out that submarine groundwater discharge is a major source of iron to marine ecosystems.


3. "Alkaline neutralizing capacity".

The useful paper with the abstract at the top of the post was brought to our attention, supposedly, because it would debunk the claim that "No credible scientist would call ANYTHING 'alkaline neutralizing capacity'".

Of course, the paper itself never suggests the existence of such a term.

But it was an honest mistake.

It turns out that the paper hadn't been seen by the person who cited it.

There was therefore no way he could have known that the assumption about what it would reveal was false.

It was not a deliberate lie.

Just a very ignorant false assumption.
18-05-2023 09:16
IBdaMannProfile picture★★★★★
(14321)
Im a BM wrote:Many organic acid anions can form strong complexes with iron - either in ferric iron(III) or ferrous iron(II) form.

Why is ferrous iron more reactive than ferric iron when ferric iron has the greater positive charge?

Im a BM wrote:A pH 4.75 acetate buffer can have 500 times as much alkalinity as sea water. Low pH does not necessarily mean low alkalinity.

OK, this is a new one for me. Why does the alkalinity not neutralize the acidity and bring the pH back above 7.0?
RE: legitimate question deserves response18-05-2023 09:46
Im a BM
★★★☆☆
(595)
IBdaMann wrote:
Im a BM wrote:Many organic acid anions can form strong complexes with iron - either in ferric iron(III) or ferrous iron(II) form.

Why is ferrous iron more reactive than ferric iron when ferric iron has the greater positive charge?

Im a BM wrote:A pH 4.75 acetate buffer can have 500 times as much alkalinity as sea water. Low pH does not necessarily mean low alkalinity.

OK, this is a new one for me. Why does the alkalinity not neutralize the acidity and bring the pH back above 7.0?



-------------------------------------------------------------------------------

Legitimate questions deserve a response.


The first one, I don't get.

I'm pretty sure I never said ferrous iron is more reactive than ferric iron.

Ferric iron is FAR more reactive, due to its greater positive charge, than ferrous iron, in terms of forming precipitates with hydroxide.

That is why ferrous iron can be soluble at sea water pH, while ferric iron cannot.

Ferrous iron is more reactive than ferric iron in terms of potential oxidation.

Microorganisms can make a living off the energy released by using oxygen to transform ferrous iron to ferric iron. Ferric iron cannot oxidize further.

Even in terms of forming complexes with organic anions, ferric iron is more reactive. Precisely because it has greater positive charge.



The second question.

A pH 4.75 acetate buffer has equal number of acetate ions as it has molecules of (not dissociated) acetic acid.

Why does the alkalinity not neutralize the acidity and raise the pH.

Well there is a lot of acetic acid, but there isn't much acidity. pH 4.75 isn't that low. Many beverages are a hundred times as acidic.

The acetic acid is not dissociated. It has not released its hydrogen ions into solution.

A strong acid - hydrochloric, sulfuric, nitric, etc., will dissociate virtually 100% into hydrogen ions and (chloride, sulfate, nitrate, etc.) anions.

Chloride, sulfate, and nitrate are worthless as buffers. You can't force a proton back on to them unless the pH is ridiculously low.

Weak acids make good buffers. Acetic acid, like carbonic acid, is a weak acid.

The anions of weak acids make good buffers - like the bicarbonate and carbonate ions in sea water.

In the acetate buffer at pH 4.75, the acetic acid will not dissociate to release hydrogen into solution unless something RAISES the pH.

The acetate will not accept a proton to become acetic acid unless something LOWERS the pH.

So, its a 50-50 mix at a Mexican standoff. There is no way the pH is going to spontaneously shift because one of them somehow changes the other.

One more fun fact. Since this buffer pH is precisely at the pka of acetic acid, this is where the buffer will have maximum strength to resist pH shift in either direction, upon addition of either hydrogen ions or hydroxide ions.
18-05-2023 10:04
IBdaMannProfile picture★★★★★
(14321)
Im a BM wrote:The first one, I don't get.

I'm pretty sure I never said ferrous iron is more reactive than ferric iron.

Correct. You didn't. I was reading your post and I was a little curious about the ferrous iron and the ferric iron so I read up a little on those. Then I decided to ask ChatGPT a few questions about something else, and it was ChatGPT that went into great detail about how ferrous iron is more reactive than ferric iron.

ChatGT wrote: Ferrous iron (Fe2+) refers to iron in its reduced state, meaning it has lost two electrons and has a positive 2 charge. It is commonly found in compounds such as ferrous sulfate (FeSO4) and ferrous chloride (FeCl2). Ferrous iron is generally more soluble in water and tends to be more reactive than ferric iron.

Ferric iron (Fe3+), on the other hand, refers to iron in its oxidized state, meaning it has lost three electrons and has a positive 3 charge. It is commonly found in compounds such as ferric oxide (Fe2O3) and ferric chloride (FeCl3). Ferric iron is less soluble in water and is generally less reactive than ferrous iron.

The difference in oxidation state between ferrous iron and ferric iron has implications for their chemical and biological properties. For example, ferric iron is often involved in redox reactions and can act as an electron acceptor in biological processes. In contrast, ferrous iron is more easily oxidized to ferric iron and can participate in electron transfer reactions.

Overall, the main distinction between ferric iron and ferrous iron lies in their oxidation states, which affect their solubility, reactivity, and roles in various chemical and biological processes.

IBDaMann asked ChatGT: how can ferric iron be less reactive than ferrous iron? Ferric iron has a greater charge?

ChatGPT responded: I apologize for any confusion caused by my previous response. You are correct that ferric iron has a greater charge compared to ferrous iron. However, it is more accurate to say that ferric iron is generally less reactive in certain contexts, while ferrous iron is more readily involved in redox reactions.

The reactivity of iron ions depends on the specific chemical environment and the nature of the reactions involved. In general, ferrous iron (Fe2+) is more reactive because it is more easily oxidized to ferric iron (Fe3+). This oxidation process involves the loss of an electron. Ferrous iron can readily donate electrons and participate in redox reactions, acting as a reducing agent.

Ferric iron, with its higher charge, is less reactive in terms of donating electrons. It is more likely to act as an electron acceptor and undergo reduction reactions, gaining electrons to be converted back to ferrous iron. However, ferric iron can still exhibit reactivity in certain contexts, particularly as an oxidizing agent or in coordination chemistry.

It's important to note that the reactivity of iron ions is influenced by numerous factors, such as pH, the presence of ligands or complexing agents, and the specific reactions and compounds involved. Therefore, while ferric iron is generally considered less reactive in terms of electron donation, its reactivity can vary depending on the circumstances.


Im a BM wrote:Ferric iron is FAR more reactive, due to its greater positive charge, than ferrous iron, in terms of forming precipitates with hydroxide.

So it would seem that we have found another ChatGPT problem. You should ask it questions on this matter and get it to go around in circles. It's therapeutic.
RE: carbonic acid, bicarbonate, carbonate buffer system19-05-2023 13:13
Im a BM
★★★☆☆
(595)
Sea water is buffered by the "carbonate system"

It is an equilibrium between three different inorganic carbon compounds.

carbonic acid H2CO3
bicarbonate ion HCO3(-)
carbonate ion CO3(2-)

The first equilibria H2CO3 = H(+) + HCO3(-) pka = 6.37

The second equilibria HCO3(-) = H(+) + CO3(-) pKa = 10.32

Sea water typically has pH close to 8.3

Applying the first equilibria, what would happen if enough hydrogen ion is added to lower sea water pH to 6.37? (the pka of the first equilbrium)

This would cause enough bicarbonate to become carbonic acid that there would be exactly equal concentrations of carbonic acid and bicarbonate ion.

Applying the second equilibria, what would happen if enough hydroxide ion is added to raise sea water pH to 10.32? (the pka of the second equilibria)

This would cause enough bicarbonate ion to become carbonate ion that there would be exactly equal concentrations of bicarbonate and carbonate.

What would happen if instead of adding hydrogen ion or hydroxide ion, we add more carbonic acid to the sea water, like when the atmospheric concentration of CO2 increases?

To maintain equilibrium, much of the additional carbonic acid would be forced to dissociate into hydrogen ion and bicarbonate ion. The extra hydrogen ions cannot get neutralized by bicarbonate because that would just drive carbonic acid concentration back up, out of equilibrium.

So, the extra hydrogen ion gets neutralized by carbonate instead, transforming it into bicarbonate.

The net effect of all this buffering is that the added carbon dioxide doesn't change the pH much at all, but it does remove carbonate from solution.

And sea creatures cannot form calcium carbonate shell unless they acquire sufficient carbonate ions from sea water.

They call it "acidification" even though the pH barely decreases.

The harm is caused by the depletion of carbonate alkalinity, reducing the concentration of bioavailable carbonate ions.
19-05-2023 17:02
IBdaMannProfile picture★★★★★
(14321)
Im a BM wrote:What would happen if instead of adding hydrogen ion or hydroxide ion, we add more carbonic acid to the sea water, like when the atmospheric concentration of CO2 increases?

This question carries two fallacies that must be assumed in order to proceed with your point:

1. This question assumes that atmospheric CO2 levels are increasing. CO2 is heavier than either O2 or N2. CO2 falls to ground/sea-level where the plants are and is greedily consumed as plant food. There is no reason any rational adult should believe that atmospheric CO2 levels are somehow increasing.

2. The "What would happen" part of the question assumes an increasing accumulation of carbonic acid in the ocean. Seawater evaporation, which never ceases, is continually eliminating carbonic acid from the ocean and is a persistent force for making the ocean more alkaline.

For the sake of discussion, I will assume these fallacies as being true, and "realize" that the ocean is losing its alkalinity.

You then postulate that this is a bad thing and that we must find ways to restore alkalinity to the ocean.

Therefore, if we assume the two fallacies above, we ultimately arrive at the question "Is the ocean's loss of alkalinity a bad thing?" Most rational adults would find the intuitive answer to be that it is, in fact, a very good thing. Life is mostly acidic. High pH is mostly reserved for industrial chemicals. Where ocean pH tends to be lowest, i.e. where freshwater runoff is received, there is far greater diversity of thriving sea life. This realization leads to the conclusion that alkalinity loss is a good thing and should be allowed to proceed.

You, however, claim otherwise. Would you mind elaborating?
21-05-2023 01:29
James_
★★★★☆
(1982)
Im a BM wrote:
Sea water is buffered by the "carbonate system"

It is an equilibrium between three different inorganic carbon compounds.

carbonic acid H2CO3
bicarbonate ion HCO3(-)
carbonate ion CO3(2-)

The first equilibria H2CO3 = H(+) + HCO3(-) pka = 6.37

The second equilibria HCO3(-) = H(+) + CO3(-) pKa = 10.32

Sea water typically has pH close to 8.3

Applying the first equilibria, what would happen if enough hydrogen ion is added to lower sea water pH to 6.37? (the pka of the first equilbrium)

This would cause enough bicarbonate to become carbonic acid that there would be exactly equal concentrations of carbonic acid and bicarbonate ion.

Applying the second equilibria, what would happen if enough hydroxide ion is added to raise sea water pH to 10.32? (the pka of the second equilibria)

This would cause enough bicarbonate ion to become carbonate ion that there would be exactly equal concentrations of bicarbonate and carbonate.

What would happen if instead of adding hydrogen ion or hydroxide ion, we add more carbonic acid to the sea water, like when the atmospheric concentration of CO2 increases?

To maintain equilibrium, much of the additional carbonic acid would be forced to dissociate into hydrogen ion and bicarbonate ion. The extra hydrogen ions cannot get neutralized by bicarbonate because that would just drive carbonic acid concentration back up, out of equilibrium.

So, the extra hydrogen ion gets neutralized by carbonate instead, transforming it into bicarbonate.

The net effect of all this buffering is that the added carbon dioxide doesn't change the pH much at all, but it does remove carbonate from solution.

And sea creatures cannot form calcium carbonate shell unless they acquire sufficient carbonate ions from sea water.

They call it "acidification" even though the pH barely decreases.

The harm is caused by the depletion of carbonate alkalinity, reducing the concentration of bioavailable carbonate ions.



You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?
21-05-2023 02:43
SwanProfile picture★★★★★
(5628)
James_ wrote:
Im a BM wrote:
Sea water is buffered by the "carbonate system"

It is an equilibrium between three different inorganic carbon compounds.

carbonic acid H2CO3
bicarbonate ion HCO3(-)
carbonate ion CO3(2-)

The first equilibria H2CO3 = H(+) + HCO3(-) pka = 6.37

The second equilibria HCO3(-) = H(+) + CO3(-) pKa = 10.32

Sea water typically has pH close to 8.3

Applying the first equilibria, what would happen if enough hydrogen ion is added to lower sea water pH to 6.37? (the pka of the first equilbrium)

This would cause enough bicarbonate to become carbonic acid that there would be exactly equal concentrations of carbonic acid and bicarbonate ion.

Applying the second equilibria, what would happen if enough hydroxide ion is added to raise sea water pH to 10.32? (the pka of the second equilibria)

This would cause enough bicarbonate ion to become carbonate ion that there would be exactly equal concentrations of bicarbonate and carbonate.

What would happen if instead of adding hydrogen ion or hydroxide ion, we add more carbonic acid to the sea water, like when the atmospheric concentration of CO2 increases?

To maintain equilibrium, much of the additional carbonic acid would be forced to dissociate into hydrogen ion and bicarbonate ion. The extra hydrogen ions cannot get neutralized by bicarbonate because that would just drive carbonic acid concentration back up, out of equilibrium.

So, the extra hydrogen ion gets neutralized by carbonate instead, transforming it into bicarbonate.

The net effect of all this buffering is that the added carbon dioxide doesn't change the pH much at all, but it does remove carbonate from solution.

And sea creatures cannot form calcium carbonate shell unless they acquire sufficient carbonate ions from sea water.

They call it "acidification" even though the pH barely decreases.

The harm is caused by the depletion of carbonate alkalinity, reducing the concentration of bioavailable carbonate ions.



You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?


What planet are you on?


IBdaMann claims that Gold is a molecule, and that the last ice age never happened because I was not there to see it. The only conclusion that can be drawn from this is that IBdaMann is clearly not using enough LSD.

According to CDC/Government info, people who were vaccinated are now DYING at a higher rate than non-vaccinated people, which exposes the covid vaccines as the poison that they are, this is now fully confirmed by the terrorist CDC

This place is quieter than the FBI commenting on the chink bank account information on Hunter Xiden's laptop

I LOVE TRUMP BECAUSE HE PISSES OFF ALL THE PEOPLE THAT I CAN'T STAND.

ULTRA MAGA

"Being unwanted, unloved, uncared for, forgotten by everybody, I think that is a much greater hunger, a much greater poverty than the person who has nothing to eat." MOTHER THERESA OF CALCUTTA

So why is helping to hide the murder of an American president patriotic?


It's time to dig up Joseph Mccarthey and show him TikTok, then duck.


Now be honest, was I correct or was I correct? LOL
21-05-2023 03:08
James_
★★★★☆
(1982)
Swan wrote:


You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?



Carbonic acid is a hypothetical gas which cannot exist. That's basic knowledge
and is a part of what my research is based on.
Edited on 21-05-2023 03:09
21-05-2023 03:14
James_
★★★★☆
(1982)
@IBDM, with carbonic acid, just not what my research is about but can explain. It's like what is the Salish Sea and why does ITN care? Just not my concern.
With acidity in the ocean, is that because of the gasses that carbonic acid allows for? Acidity suggests a chemical reaction. What reactions are occurring to determine acidity?

p.s., my post was acidic to ITN, there is no Salish Sea.
Edited on 21-05-2023 03:16
21-05-2023 03:43
HarveyH55Profile picture★★★★★
(5191)
IBdaMann wrote:
Im a BM wrote:What would happen if instead of adding hydrogen ion or hydroxide ion, we add more carbonic acid to the sea water, like when the atmospheric concentration of CO2 increases?

This question carries two fallacies that must be assumed in order to proceed with your point:

1. This question assumes that atmospheric CO2 levels are increasing. CO2 is heavier than either O2 or N2. CO2 falls to ground/sea-level where the plants are and is greedily consumed as plant food. There is no reason any rational adult should believe that atmospheric CO2 levels are somehow increasing.

2. The "What would happen" part of the question assumes an increasing accumulation of carbonic acid in the ocean. Seawater evaporation, which never ceases, is continually eliminating carbonic acid from the ocean and is a persistent force for making the ocean more alkaline.

For the sake of discussion, I will assume these fallacies as being true, and "realize" that the ocean is losing its alkalinity.

You then postulate that this is a bad thing and that we must find ways to restore alkalinity to the ocean.

Therefore, if we assume the two fallacies above, we ultimately arrive at the question "Is the ocean's loss of alkalinity a bad thing?" Most rational adults would find the intuitive answer to be that it is, in fact, a very good thing. Life is mostly acidic. High pH is mostly reserved for industrial chemicals. Where ocean pH tends to be lowest, i.e. where freshwater runoff is received, there is far greater diversity of thriving sea life. This realization leads to the conclusion that alkalinity loss is a good thing and should be allowed to proceed.

You, however, claim otherwise. Would you mind elaborating?


Most life on this planet is tolerant to small changes in pH, and adapt pretty well. Life is good, where fresh water runs off into the oceans, because it's not exactly 'fresh' by the time it reaches the ocean. Lot of it starts the journey in high up in the mountains, and drags all kinds of crap downstream. Yeah, even actual feces, but there are a lot of nutrients for plants, organic stuff from rotting plants, fish, animals. Sometimes the mob still dump dead bodies in water. 'Fresh water' is really high in nutritional stuff, which makes for easy food for water critters. Bonus, coastal waters are shallow, which helps protect the feeder fish, from the larger fish.
21-05-2023 03:52
SwanProfile picture★★★★★
(5628)
James_ wrote:
Swan wrote:


You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?



Carbonic acid is a hypothetical gas which cannot exist. That's basic knowledge
and is a part of what my research is based on.


Oh you are on Pluto and Carbonic acid is hypothetical there, well I have never left the Earth, besides that one dead concert, so I have no comments on Pluto where you are.


IBdaMann claims that Gold is a molecule, and that the last ice age never happened because I was not there to see it. The only conclusion that can be drawn from this is that IBdaMann is clearly not using enough LSD.

According to CDC/Government info, people who were vaccinated are now DYING at a higher rate than non-vaccinated people, which exposes the covid vaccines as the poison that they are, this is now fully confirmed by the terrorist CDC

This place is quieter than the FBI commenting on the chink bank account information on Hunter Xiden's laptop

I LOVE TRUMP BECAUSE HE PISSES OFF ALL THE PEOPLE THAT I CAN'T STAND.

ULTRA MAGA

"Being unwanted, unloved, uncared for, forgotten by everybody, I think that is a much greater hunger, a much greater poverty than the person who has nothing to eat." MOTHER THERESA OF CALCUTTA

So why is helping to hide the murder of an American president patriotic?


It's time to dig up Joseph Mccarthey and show him TikTok, then duck.


Now be honest, was I correct or was I correct? LOL
21-05-2023 04:03
James_
★★★★☆
(1982)
Swan wrote:
James_ wrote:
Swan wrote:


You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?



Carbonic acid is a hypothetical gas which cannot exist. That's basic knowledge
and is a part of what my research is based on.


Oh you are on Pluto and Carbonic acid is hypothetical there, well I have never left the Earth, besides that one dead concert, so I have no comments on Pluto where you are.



And some guy said that the Earth revolves around the Sun. Are you serious?
21-05-2023 04:07
SwanProfile picture★★★★★
(5628)
James_ wrote:
Swan wrote:
James_ wrote:
Swan wrote:


You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?



Carbonic acid is a hypothetical gas which cannot exist. That's basic knowledge
and is a part of what my research is based on.


Oh you are on Pluto and Carbonic acid is hypothetical there, well I have never left the Earth, besides that one dead concert, so I have no comments on Pluto where you are.



And some guy said that the Earth revolves around the Sun. Are you serious?


The moon revolves around the earth, which revolves around the sun which revolves around the galactic core which is moving through space. Pretty neat all said


IBdaMann claims that Gold is a molecule, and that the last ice age never happened because I was not there to see it. The only conclusion that can be drawn from this is that IBdaMann is clearly not using enough LSD.

According to CDC/Government info, people who were vaccinated are now DYING at a higher rate than non-vaccinated people, which exposes the covid vaccines as the poison that they are, this is now fully confirmed by the terrorist CDC

This place is quieter than the FBI commenting on the chink bank account information on Hunter Xiden's laptop

I LOVE TRUMP BECAUSE HE PISSES OFF ALL THE PEOPLE THAT I CAN'T STAND.

ULTRA MAGA

"Being unwanted, unloved, uncared for, forgotten by everybody, I think that is a much greater hunger, a much greater poverty than the person who has nothing to eat." MOTHER THERESA OF CALCUTTA

So why is helping to hide the murder of an American president patriotic?


It's time to dig up Joseph Mccarthey and show him TikTok, then duck.


Now be honest, was I correct or was I correct? LOL
21-05-2023 04:17
James_
★★★★☆
(1982)
Swan wrote:
James_ wrote:
Swan wrote:
James_ wrote:
Swan wrote:


You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?



Carbonic acid is a hypothetical gas which cannot exist. That's basic knowledge
and is a part of what my research is based on.


Oh you are on Pluto and Carbonic acid is hypothetical there, well I have never left the Earth, besides that one dead concert, so I have no comments on Pluto where you are.



And some guy said that the Earth revolves around the Sun. Are you serious?


The moon revolves around the earth, which revolves around the sun which revolves around the galactic core which is moving through space. Pretty neat all said


And next you'll say the uni has a precession. God what a bunch of lobster ****s ya'all are.
21-05-2023 13:04
SwanProfile picture★★★★★
(5628)
James_ wrote:
Swan wrote:
James_ wrote:
Swan wrote:
James_ wrote:
Swan wrote:


You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?



Carbonic acid is a hypothetical gas which cannot exist. That's basic knowledge
and is a part of what my research is based on.


Oh you are on Pluto and Carbonic acid is hypothetical there, well I have never left the Earth, besides that one dead concert, so I have no comments on Pluto where you are.



And some guy said that the Earth revolves around the Sun. Are you serious?


The moon revolves around the earth, which revolves around the sun which revolves around the galactic core which is moving through space. Pretty neat all said


And next you'll say the uni has a precession. God what a bunch of lobster ****s ya'all are.


The Universe is undefined, at least to humanity


IBdaMann claims that Gold is a molecule, and that the last ice age never happened because I was not there to see it. The only conclusion that can be drawn from this is that IBdaMann is clearly not using enough LSD.

According to CDC/Government info, people who were vaccinated are now DYING at a higher rate than non-vaccinated people, which exposes the covid vaccines as the poison that they are, this is now fully confirmed by the terrorist CDC

This place is quieter than the FBI commenting on the chink bank account information on Hunter Xiden's laptop

I LOVE TRUMP BECAUSE HE PISSES OFF ALL THE PEOPLE THAT I CAN'T STAND.

ULTRA MAGA

"Being unwanted, unloved, uncared for, forgotten by everybody, I think that is a much greater hunger, a much greater poverty than the person who has nothing to eat." MOTHER THERESA OF CALCUTTA

So why is helping to hide the murder of an American president patriotic?


It's time to dig up Joseph Mccarthey and show him TikTok, then duck.


Now be honest, was I correct or was I correct? LOL
RE: recap21-05-2023 20:26
Im a BM
★★★☆☆
(595)
Im a BM wrote:
IBdaMann wrote:
Im a BM wrote:[quote]IBdaMann wrote:Would you define acidity as "alkaline neutralizing capacity"?
No trained scientist would call ANYTHING "alkaline neutralizing capacity"

What if, perchance, one is found?


Environ. Sci. Technol.1990,24,1486-1489
Acid Neutralizing Capacity, Alkalinity, and Acid-Base Status of Natural Waters Containing Organic Acids

Harold F. Hemond
Water Resources and Environmental Engineering, Department of Civil Engineering, and Massachusetts Institute of Technology Energy Laboratory, Cambridge, Massachusetts 02139

Downloaded by MIT on October 2, 2009 [url]http://pubs.acs.orgPublicationDate
ctober1,1990|doi:10.1021/es00080a005[/url]

The terms acid neutralizing capacity (ANC) and alkalinity (Alk) are extensively employed in the characterization of natural waters, including soft circumneutral oracidic waters. However, in the presence of organic acids, ANC measurements are inconsistent with many conceptual definitions of ANC or Alk and do not provide an adequate characterization of the acid-base chemistry of water.


------------------------------------------------------------------------------

This paper does not call anything "alkaline neutralizing capacity".

It DOES give good background on "The terms acid neutralizing capacity (ANC) and alkalinity (Alk)..." Recommended reading for those who have difficulty with these definitions.

But what is special about the paper is recognition that organic alkalinity is a not a negligible contributor to total alkalinity. Indeed, our understanding of alkalinity is incomplete without it.

Historically, the only measurement done was total alkalinity. Without knowing which anions were responsible, it was a simple titration with acid to reach a designated endpoint pH.

Later, it was recognized that there was value in more complete characterization of the species involved. Four categories of alkalinity were reported.
total alkalinity - indiscriminate measure of all acid neutralizing anions.
hydroxide alkalinity - that portion of total alkalinity supplied by hydroxide ions. Usually a tiny, tiny fraction of the total.
bicarbonate alkalinity - the lion's share of total alkalinity in most waters, supplied by bicarbonate ions.
carbonate alkalinity - the much smaller fraction of total alkalinity supplied by carbonate ions.

While it was known that other anions, such as phosphate, contributed to alkalinity, they were usually such a small fraction of the total, they were dismissed as negligible.

This paper points out that anions of organic acids should not be ignored.

Example: acetic acid (vinegar) has a pKa of about 4.75. This means that if a solution of acetic acid is adjusted to pH 4.75, exactly half of it will be dissociated into hydrogen ions and citrate ions. The other half remains undissociated citric acid - proton remaining attached rather than free in solution.

In contrast, hydrochloric acid has a pKa of -6.3
This means that the pH would have to somehow be driven down to -6.3 in order to get half the hydrogen ions to reattach to chloride and form intact hydrochloric acid.

To create pH below zero is possible, but almost never occurs in nature.

Chloride ions provide no alkalinity because they won't neutralize any acid until the pH is well below zero.

Acetic acid and its associated acetate ions, on the other hand, can be used to neutralize acidity at near neutral pH. Acetate buffers are used in chemistry.

So, it turns out that anions of organic acids are a much more important contributor to alkalinity than previously believed.

And they can do something very special that few other anions can.

Many organic acid anions can form strong complexes with iron - either in ferric iron(III) or ferrous iron(II) form.

Iron is a limiting nutrient in sea water.

Organic alkalinity is responsible for making iron available to support photosynthesis in the sea.
RE: recap21-05-2023 20:28
Im a BM
★★★☆☆
(595)
-------------------------------------------------------------------------------

1. Erratum

The above post mistakenly (dyslexically) says "citric acid" and "citrate" in a couple of places where it should say "acetic acid" and "acetate".

Acetate buffer with low pH and high alkalinity.

Sea water has from about 0.002 - 0.0025 moles/liter alkalinity

An acetate buffer made from 2 molar acetic acid, adjusted to pH 4.75 with sodium hydroxide, will contain 1 mole per liter acetic acid and 1 mole per liter sodium acetate. The acetate anion provides 1 mole per liter alkalinity.

A pH 4.75 acetate buffer can have 500 times as much alkalinity as sea water.
Low pH does not necessarily mean low alkalinity.



2. Iron, iron everywhere, and not a drop to drink.

Iron is one of the most abundant elements found in sea floor sediments.

Iron is one of the most scarce elements found in sea water.

Nearly all the iron entering the sea comes in as solid particulates of ferric iron clay minerals. They are insoluble at sea water pH. Sink to the bottom and stay there.

Some of the iron entering sea water is in dissolved form.

Nearly all of it precipitates out into insoluble form.

Dissolved ferric iron immediately drops out to form insoluble ferric hydroxides.

Dissolved ferrous iron can remain soluble at sea water pH.

But it is readily oxidized in the presence of free oxygen by bacteria to form insoluble ferric iron.

Pretty much the only iron that can stay dissolved in sea water is bound to organic anions in chelation complexes. Literally, 99% of dissolved iron in sea water is complexed by organic anions.

Ferrous iron cannot be oxidized to ferric iron with its reactive sites occluded by organic ligands.

Ferric iron cannot form precipitates with hydroxide when its reactive sites are occluded by organic ligands.

And it turns out that submarine groundwater discharge is a major source of iron to marine ecosystems.


3. "Alkaline neutralizing capacity".

The useful paper with the abstract at the top of the post was brought to our attention, supposedly, because it would debunk the claim that "No credible scientist would call ANYTHING 'alkaline neutralizing capacity'".

Of course, the paper itself never suggests the existence of such a term.

But it was an honest mistake.

It turns out that the paper hadn't been seen by the person who cited it.

There was therefore no way he could have known that the assumption about what it would reveal was false.

It was not a deliberate lie.

Just a very ignorant false assumption.[/quote]
RE: recap21-05-2023 20:28
Im a BM
★★★☆☆
(595)
Im a BM wrote:
IBdaMann wrote:
Im a BM wrote:Many organic acid anions can form strong complexes with iron - either in ferric iron(III) or ferrous iron(II) form.

Why is ferrous iron more reactive than ferric iron when ferric iron has the greater positive charge?

Im a BM wrote:A pH 4.75 acetate buffer can have 500 times as much alkalinity as sea water. Low pH does not necessarily mean low alkalinity.

OK, this is a new one for me. Why does the alkalinity not neutralize the acidity and bring the pH back above 7.0?



-------------------------------------------------------------------------------

Legitimate questions deserve a response.


The first one, I don't get.

I'm pretty sure I never said ferrous iron is more reactive than ferric iron.

Ferric iron is FAR more reactive, due to its greater positive charge, than ferrous iron, in terms of forming precipitates with hydroxide.

That is why ferrous iron can be soluble at sea water pH, while ferric iron cannot.

Ferrous iron is more reactive than ferric iron in terms of potential oxidation.

Microorganisms can make a living off the energy released by using oxygen to transform ferrous iron to ferric iron. Ferric iron cannot oxidize further.

Even in terms of forming complexes with organic anions, ferric iron is more reactive. Precisely because it has greater positive charge.



The second question.

A pH 4.75 acetate buffer has equal number of acetate ions as it has molecules of (not dissociated) acetic acid.

Why does the alkalinity not neutralize the acidity and raise the pH.

Well there is a lot of acetic acid, but there isn't much acidity. pH 4.75 isn't that low. Many beverages are a hundred times as acidic.

The acetic acid is not dissociated. It has not released its hydrogen ions into solution.

A strong acid - hydrochloric, sulfuric, nitric, etc., will dissociate virtually 100% into hydrogen ions and (chloride, sulfate, nitrate, etc.) anions.

Chloride, sulfate, and nitrate are worthless as buffers. You can't force a proton back on to them unless the pH is ridiculously low.

Weak acids make good buffers. Acetic acid, like carbonic acid, is a weak acid.

The anions of weak acids make good buffers - like the bicarbonate and carbonate ions in sea water.

In the acetate buffer at pH 4.75, the acetic acid will not dissociate to release hydrogen into solution unless something RAISES the pH.

The acetate will not accept a proton to become acetic acid unless something LOWERS the pH.

So, its a 50-50 mix at a Mexican standoff. There is no way the pH is going to spontaneously shift because one of them somehow changes the other.

One more fun fact. Since this buffer pH is precisely at the pka of acetic acid, this is where the buffer will have maximum strength to resist pH shift in either direction, upon addition of either hydrogen ions or hydroxide ions.
RE: recap21-05-2023 20:29
Im a BM
★★★☆☆
(595)
Im a BM wrote:
Sea water is buffered by the "carbonate system"

It is an equilibrium between three different inorganic carbon compounds.

carbonic acid H2CO3
bicarbonate ion HCO3(-)
carbonate ion CO3(2-)

The first equilibria H2CO3 = H(+) + HCO3(-) pka = 6.37

The second equilibria HCO3(-) = H(+) + CO3(-) pKa = 10.32

Sea water typically has pH close to 8.3

Applying the first equilibria, what would happen if enough hydrogen ion is added to lower sea water pH to 6.37? (the pka of the first equilbrium)

This would cause enough bicarbonate to become carbonic acid that there would be exactly equal concentrations of carbonic acid and bicarbonate ion.

Applying the second equilibria, what would happen if enough hydroxide ion is added to raise sea water pH to 10.32? (the pka of the second equilibria)

This would cause enough bicarbonate ion to become carbonate ion that there would be exactly equal concentrations of bicarbonate and carbonate.

What would happen if instead of adding hydrogen ion or hydroxide ion, we add more carbonic acid to the sea water, like when the atmospheric concentration of CO2 increases?

To maintain equilibrium, much of the additional carbonic acid would be forced to dissociate into hydrogen ion and bicarbonate ion. The extra hydrogen ions cannot get neutralized by bicarbonate because that would just drive carbonic acid concentration back up, out of equilibrium.

So, the extra hydrogen ion gets neutralized by carbonate instead, transforming it into bicarbonate.

The net effect of all this buffering is that the added carbon dioxide doesn't change the pH much at all, but it does remove carbonate from solution.

And sea creatures cannot form calcium carbonate shell unless they acquire sufficient carbonate ions from sea water.

They call it "acidification" even though the pH barely decreases.

The harm is caused by the depletion of carbonate alkalinity, reducing the concentration of bioavailable carbonate ions.
22-05-2023 22:08
Into the NightProfile picture★★★★★
(21490)
Im a BM wrote:
Sea water is buffered by the "carbonate system"

Water is in and of itself a buffer.
Im a BM wrote:
It is an equilibrium between three different inorganic carbon compounds.

carbonic acid H2CO3
bicarbonate ion HCO3(-)
carbonate ion CO3(2-)

The first equilibria H2CO3 = H(+) + HCO3(-) pka = 6.37

The second equilibria HCO3(-) = H(+) + CO3(-) pKa = 10.32

Sea water typically has pH close to 8.3

Manufactured numbers. Argument from randU fallacy. The pH of the oceans is unknown. It is, however, alkaline.
Im a BM wrote:
...deleted numerous verbose 'what if' BS...
The net effect of all this buffering is that the added carbon dioxide doesn't change the pH much at all, but it does remove carbonate from solution.

Carbonate is not a chemical. There is no such thing as 'carbonate in solution'.
Im a BM wrote:
And sea creatures cannot form calcium carbonate shell unless they acquire sufficient carbonate ions from sea water.

They are having no problem building their shells.
Im a BM wrote:
They call it "acidification" even though the pH barely decreases.

You cannot acidify an alkaline. The pH of the oceans is unknown. It is not uniform throughout the world's oceans.
Im a BM wrote:
The harm is caused by the depletion of carbonate alkalinity, reducing the concentration of bioavailable carbonate ions.

Carbonate is not a chemical. There is no such thing as 'carbonate alkalinity'. There is no such thing as 'bioavailable carbonate ions'. All carbonate ions are the same.


The Parrot Killer

Debunked in my sig. - tmiddles

Google keeps track of paranoid talk and i'm not on their list. I've been evaluated and certified. - keepit

nuclear powered ships do not require nuclear fuel. - Swan

While it is true that fossils do not burn it is also true that fossil fuels burn very well - Swan
22-05-2023 22:14
Into the NightProfile picture★★★★★
(21490)
James_ wrote:
Swan wrote:


You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?



Carbonic acid is a hypothetical gas which cannot exist. That's basic knowledge
and is a part of what my research is based on.

It is not a hypothetical gas.


The Parrot Killer

Debunked in my sig. - tmiddles

Google keeps track of paranoid talk and i'm not on their list. I've been evaluated and certified. - keepit

nuclear powered ships do not require nuclear fuel. - Swan

While it is true that fossils do not burn it is also true that fossil fuels burn very well - Swan
22-05-2023 22:20
Into the NightProfile picture★★★★★
(21490)
James_ wrote:
@IBDM, with carbonic acid, just not what my research is about but can explain. It's like what is the Salish Sea and why does ITN care? Just not my concern.
With acidity in the ocean, is that because of the gasses that carbonic acid allows for? Acidity suggests a chemical reaction. What reactions are occurring to determine acidity?

p.s., my post was acidic to ITN, there is no Salish Sea.

The Salish Sea consists of Puget Sound, the Straits of Juan de Fuca and Georgia, and various interconnecting waterways. It is still called the Salish Sea.

Acidity is not a chemical reaction.


The Parrot Killer

Debunked in my sig. - tmiddles

Google keeps track of paranoid talk and i'm not on their list. I've been evaluated and certified. - keepit

nuclear powered ships do not require nuclear fuel. - Swan

While it is true that fossils do not burn it is also true that fossil fuels burn very well - Swan
22-05-2023 22:24
Into the NightProfile picture★★★★★
(21490)
Swan wrote:
James_ wrote:
Swan wrote:
James_ wrote:
Swan wrote:


You're right but none of you know why. Carbonic acid can't exist. Why?
What determines/prevents carbonic acid from occurring?



Carbonic acid is a hypothetical gas which cannot exist. That's basic knowledge
and is a part of what my research is based on.


Oh you are on Pluto and Carbonic acid is hypothetical there, well I have never left the Earth, besides that one dead concert, so I have no comments on Pluto where you are.



And some guy said that the Earth revolves around the Sun. Are you serious?


The moon revolves around the earth, which revolves around the sun which revolves around the galactic core which is moving through space. Pretty neat all said

The Moon does not revolve around the Earth, and the Earth does not revolve around the Sun, and the Sun does not revolve around the galaxy.

The galaxy is not inside the Sun, nor is the Sun inside the Earth, nor is the Earth inside the Moon.


The Parrot Killer

Debunked in my sig. - tmiddles

Google keeps track of paranoid talk and i'm not on their list. I've been evaluated and certified. - keepit

nuclear powered ships do not require nuclear fuel. - Swan

While it is true that fossils do not burn it is also true that fossil fuels burn very well - Swan
22-05-2023 22:27
Into the NightProfile picture★★★★★
(21490)
Im a BM wrote:
Im a BM wrote:
IBdaMann wrote:
Im a BM wrote:Many organic acid anions can form strong complexes with iron - either in ferric iron(III) or ferrous iron(II) form.

Why is ferrous iron more reactive than ferric iron when ferric iron has the greater positive charge?

Im a BM wrote:A pH 4.75 acetate buffer can have 500 times as much alkalinity as sea water. Low pH does not necessarily mean low alkalinity.

OK, this is a new one for me. Why does the alkalinity not neutralize the acidity and bring the pH back above 7.0?



-------------------------------------------------------------------------------

Legitimate questions deserve a response.


The first one, I don't get.

I'm pretty sure I never said ferrous iron is more reactive than ferric iron.

Ferric iron is FAR more reactive, due to its greater positive charge, than ferrous iron, in terms of forming precipitates with hydroxide.

That is why ferrous iron can be soluble at sea water pH, while ferric iron cannot.

Ferrous iron is more reactive than ferric iron in terms of potential oxidation.

Microorganisms can make a living off the energy released by using oxygen to transform ferrous iron to ferric iron. Ferric iron cannot oxidize further.

Even in terms of forming complexes with organic anions, ferric iron is more reactive. Precisely because it has greater positive charge.



The second question.

A pH 4.75 acetate buffer has equal number of acetate ions as it has molecules of (not dissociated) acetic acid.

Why does the alkalinity not neutralize the acidity and raise the pH.

Well there is a lot of acetic acid, but there isn't much acidity. pH 4.75 isn't that low. Many beverages are a hundred times as acidic.

The acetic acid is not dissociated. It has not released its hydrogen ions into solution.

A strong acid - hydrochloric, sulfuric, nitric, etc., will dissociate virtually 100% into hydrogen ions and (chloride, sulfate, nitrate, etc.) anions.

Chloride, sulfate, and nitrate are worthless as buffers. You can't force a proton back on to them unless the pH is ridiculously low.

Weak acids make good buffers. Acetic acid, like carbonic acid, is a weak acid.

The anions of weak acids make good buffers - like the bicarbonate and carbonate ions in sea water.

In the acetate buffer at pH 4.75, the acetic acid will not dissociate to release hydrogen into solution unless something RAISES the pH.

The acetate will not accept a proton to become acetic acid unless something LOWERS the pH.

So, its a 50-50 mix at a Mexican standoff. There is no way the pH is going to spontaneously shift because one of them somehow changes the other.

One more fun fact. Since this buffer pH is precisely at the pka of acetic acid, this is where the buffer will have maximum strength to resist pH shift in either direction, upon addition of either hydrogen ions or hydroxide ions.


You still don't know what a buffer is. Oh well...I tried.


The Parrot Killer

Debunked in my sig. - tmiddles

Google keeps track of paranoid talk and i'm not on their list. I've been evaluated and certified. - keepit

nuclear powered ships do not require nuclear fuel. - Swan

While it is true that fossils do not burn it is also true that fossil fuels burn very well - Swan
Edited on 22-05-2023 22:28
25-05-2023 21:23
Im a BM
★★★☆☆
(595)
IBdaMann wrote:
sealover wrote:This may be the last time I reply to one of your posts.

Thank you. Thus far you have only been wasting bandwidth.

sealover wrote:Personal insults rarely win a scientific debate.

How would you know? You have never debated any science. You apparently don't know any science to debate.

You don't even know what it means to define your terms.

You don't even know the difference between science and religion.

You can't even express your supposed "point" in your own words in plain English.

You are a moron who is trying to convince intelligent people that you are somehow an expert in science. How do you think that is going to work out for you?

sealover wrote:You are right about one thing. I "don't have a degree in chemistry". That would mean I have only one such degree.

Too funny! Just after claiming that you are not expecting to garner respect based on "credentials" you try to squeeze in the above statement.

I, for one, am not buying your claims of education. You have demonstrated nothing but scientific illiteracy and really lame excuses.

Is there a reason you refuse to simply state your point in plain English for others to scrutinize? Are you ashamed of whatever position/belief that you hold?

Check your posts. No point whatsoever. No science whatsoever. No demonstration of understanding any science.

Wait! ... you did try to make one point, i.e. that flourishing plant life has created a "dead zone."

For everyone else reading this, the new Climate Change threat is "hypoxic zones" that are areas of ocean that are low on oxygen. This gets hyped to "it's a death zone that is killing fish" and becomes an urgent call to regulate, not CO2, but "nutrients." Yes, "nutrients" are now a bad thing that must be regulated by the world's governments in order to save the planet. It differs not from Global Warming. Here is an "official" description of the hypoxic ground zero in the Gulf of Mexico. It will sound all too familiar:

Scientists are forecasting this summer's Gulf of Mexico hypoxic area or "dead zone" – an area of low to no oxygen that can kill fish and other marine life – to be approximately 6,700 square miles, larger than the long-term average measured size of 5,387 square miles but substantially less than the record of 8,776 square miles set in 2017. The annual prediction is based on U.S. Geological Survey river-flow and nutrient data.

Can you spot the booolsch't?

sealover wrote:As for calling me a "liar". WTF?

How many times do you need me to repeat it?

You're a liar. I explained why. Go back and read.

sealover wrote:Sounds like you know a lot about Davis. You got my number, all right.

Do they still have the cow with the open side?

sealover wrote:It also sounds like a waste of time to try to discuss science with you.

I would greatly appreciate you ceasing and desisting pretending that you have anything to contribute in the way of a science discussion. Of course it would be a waste of time for you to pretend to lecture anyone here on science because you don't know any.

You are certainly welcome to ask questions and to learn from people who do know science, but if your definition of "try to discuss science" involves you preaching booolsch't while everyone else just responds "Amen, brother!" then yes, just sit in the corner and shut the F up.

Let's just get this out of the way. You didn't come here to learn. You came here to have everyone read your stupid document, like no one has anything better to do with his time than to become indoctrinated into the next Climate Change scam.

Prove me wrong.

=================================================


"You are a moron who is trying to convince intelligent people that you are somehow an expert in science."

"You don't even know the difference between science and religion."

"I, for one, am not buying your claims of education. You have demonstrated nothing but scientific illiteracy and really lame excuses."

"Check your posts. No point whatsoever. No science whatsoever. No demonstration of understanding any science."

"You're a liar."


Go ahead. Blame me. I've ruined what used to be "one of the Internet's best discussion sites."

At least I know that adding one drop of acid to sea water does not leave its chemistry "profoundly affected" in a way that is "exponentially" more that what happens when acid is added to pure water.

Sooner or later, someone who actually understands some chemistry will join in.
26-05-2023 17:06
IBdaMannProfile picture★★★★★
(14321)
Im a BM wrote:Go ahead. Blame me. I've ruined what used to be "one of the Internet's best discussion sites."

This is your wording, not mine. If you'd like, let's discuss this.

Im a BM wrote: At least I know that adding one drop of acid to sea water does not leave its chemistry "profoundly affected" in a way that is "exponentially" more that what happens when acid is added to pure water.

A scientist does not behave as you do. Scientists clearly define their terms up front. Scientists do not presume that everybody on planet earth uses the same jargon and acronyms that they learned and/or use. Scientists are responsible for defining all of their terms and then for communicating clearly.

You do not do this. You speak in unclear sentence fragments with little regard for the ideas that you wish to express, expecting others to be mind readers, after refusing to define any of your terms.

In short, you sow confusion and then blame the confused. How can anyone call you a scientist? I'm happy to give you a do-over or two or three but clarity should be your goal, which involves defining your terms and clearly answering questions.

Part of any scientist's job is explaining why a rational adult should accept a particular model. After every conclusion you present, I ask why any rational adult should accept it. You never answer and you never explain. Instead, you become indignant. That is how a preacher behaves, not a scientist.

Im a BM wrote:Sooner or later, someone who actually understands some chemistry will join in.

Apparently, what you need is for someone who understands math to join in and teach you some. The inverse of a logarithm is an exponential. You operate under the misconception that the exponential growth of alkalinity and acidity along the pH scale is somehow logarithmic. You get those backwards. The pH scale is the logarithm of the alkalinity/acidity. Sea water will far more powerfully neutralize acid than pure water, yet you were willing to go on record as saying that pure water has a much greater effect on acid. Perhaps your problem is that you select poor wording and misstate your questions. Perhaps your problem is that you really are abysmal at math. Either way, you make it very difficult to believe that you understand this material. Sea water is a far more powerful acid-neutralizer than pure water. How do you not know this? Who are you trying to blame for you getting it wrong? Me? I was the one who gave you the correct answer.

You took particular offence at my following observations:

IBDaMann:
You don't even know what it means to define your terms.
You don't even know the difference between science and religion.
You can't even express your supposed "point" in your own words in plain English.

Let me ask:
Will you start defining all your terms?
Have you learned the difference between science and religion?
Will you make a concerted effort to express your points in plain English using the correct words?

By the way, did you notice that nobody called to have you banned, or to have you censored?
27-05-2023 00:56
Into the NightProfile picture★★★★★
(21490)
...removing severely damaged quoting...
Im a BM wrote:

Go ahead. Blame me. I've ruined what used to be "one of the Internet's best discussion sites."

Nah. You aren't capable of doing that. You haven't contributed anything but jabberwocky spam though.
Im a BM wrote:
At least I know that adding one drop of acid to sea water does not leave its chemistry "profoundly affected" in a way that is "exponentially" more that what happens when acid is added to pure water.

Sooner or later, someone who actually understands some chemistry will join in.

I'm already here. So is IBDaMann.


The Parrot Killer

Debunked in my sig. - tmiddles

Google keeps track of paranoid talk and i'm not on their list. I've been evaluated and certified. - keepit

nuclear powered ships do not require nuclear fuel. - Swan

While it is true that fossils do not burn it is also true that fossil fuels burn very well - Swan
RE: But when the student in not teachable....27-05-2023 18:40
Im a BM
★★★☆☆
(595)
Into the Night wrote:
sealover wrote:
[quote]Into the Night wrote:
There is no such thing as an 'acid sulfate'. Pyrites occur on soil all over the world. They are also known as 'fools gold'. They are quite prevalent in the rivers of upper Idaho, which makes them sparkle in a gold color. Quite pretty.

No, pyrite doesn't become sulfuric acid. These naturally occurring minerals are a salt. You can't get energy out of nothing. You should study Gibb's law and the concept of energy required to make and break bonds in molecules.

Go learn some chemistry. You are sounding like an idiot.

Carbonate is not a system. An alkaline is not an acid. I have already described to YOU the equilibrium reaction between dissolved carbon dioxide and carbonic acid.
[quote]sealover wrote:
Carbonic acid is in equilibrium with dissolved carbonate and bicarbonate ions.

Nope. It is in equilibrium with dissolved carbon dioxide.

So you CAN repeat what I say. Very good.
sealover wrote:
The "carbonate system" is a real thing.

Carbonate is not a system.
sealover wrote:
Far more than just two players in equilibrium.

Nope. Just two.
sealover wrote:
Do you know what bicarbonate is?

HCO3. Typically a forms a salt such as NaHCO3.
sealover wrote:
Do you know that carbonic acid cannot turn into carbonate or visa versa, without first going through transformation into bicarbonate (which has it's own three-way equilbrium with the other two species)

It doesn't. It is a transition from one to the other.
sealover wrote:
Go learn some chemistry. You are sounding like an idiot.

Like I said. Take my advice. Go learn chemistry.
sealover wrote:
Your ignorance regarding pyrite is a teachable moment.

The ignorance is yours.
sealover wrote:
Pyrite forms in wetland sediments when bacteria use sulfate to oxidize organic carbon under low oxygen conditions.

Nope. Pyrite forms when bacteria deoxidize a sulfate, turning it into a sulfide. Pyrite is FeS2.
sealover wrote:
Pyrite formation and burial generates alkalinity.

You cannot 'generate' alkalinity'.
sealover wrote:
Iron oxidizing bacteria use oxygen to turn pyrite into sulfuric acid.

Wups. No hydrogen.
sealover wrote:
This is basic textbook stuff.

No. You made it up. Pyrite is a stable material. It doesn't naturally decompose. Like I said, it occurs pretty much everywhere. People used to use it in wheelock guns as a spark generator.
sealover wrote:
Iron pyrite is most common, but sulfate reduction by bacteria under low oxygen conditions can produce other kinds of pyrite as well.
sealover wrote:
Arsenic is often sequestered during pyrite formation.

Nope. No arsenic in pyrite.
sealover wrote:
Arsenian pyrite can then release soluble arsenic if the pyrite is later oxidized by aerobic conditions.

Nope. No arsenic in pyrite.
sealover wrote:
Here's the true teachable moment.

The only thing you're teaching is nonsense.
sealover wrote:
Acid mine drainage gets most of its sulfuric acid from pyrite oxidation.

There is no such thing as 'oxidation' in chemistry. Buzzword fallacy.
sealover wrote:
Acid mine drainage pH is < 3.

Argument from randU fallacy. Compositional error fallacy.
sealover wrote:
Constructed wetlands neutralize acid mine drainage.

Not necessary. Anything acidic coming out of a mine will be converted into some salt.
sealover wrote:
Sulfate reduction generates pyrite and alkalinity.

Nope. Deoxidation generate pyrite. You cannot generate alkalinity.
sealover wrote:
Groundwater discharged from constructed wetlands built to remediate acid mine drainage has pH about 7.

Groundwater is not a discharge.
sealover wrote:
A constructed saltwater wetland on the coast would not have pH < 3 acid mine drainage as input water.

Random number of type randU. Argument from randU fallacy. You are making up numbers again.
sealover wrote:
Sulfate reduction would take water sea water that is already alkaline and add more alkalinity before it is discharged as groundwater.

You can't reduce a sulfate. It's already reduced.


------------------------------------------------------------------------------

Anyone with the tiniest bit of chemistry training can see why it is pointless to discuss science with a scientifically illiterate troll.

"You can't reduce a sulfate. It's already reduced".

Sulfate reduction is the most important source of alkalinity entering the sea.

Pyrite oxidation by microorganisms is the most important source of sulfuric acid entering surface waters. "Acid mine drainage" is what it is called.

Constructed wetlands have been used for more than 50 to neutralize acid mine drainage by creating low oxygen conditions for sulfate reduction.

Coastal wetlands are a net source of acidity to the sea if they are drained, which most of them have been, because it allows oxygen to interact with pyrite.
28-05-2023 04:22
Into the NightProfile picture★★★★★
(21490)
...deleted severely damaged quoting...
Im a BM wrote:
Anyone with the tiniest bit of chemistry training can see why it is pointless to discuss science with a scientifically illiterate troll.

Since you are describing yourself, you don't see the point of my posts.
Im a BM wrote:
Sulfate reduction is the most important source of alkalinity entering the sea.

You cannot reduce a sulfate.
Im a BM wrote:
Pyrite oxidation by microorganisms is the most important source of sulfuric acid entering surface waters. "Acid mine drainage" is what it is called.

Special pleading fallacies.
Im a BM wrote:
Constructed wetlands have been used for more than 50 to neutralize acid mine drainage by creating low oxygen conditions for sulfate reduction.

You cannot reduce a sulfate. It's already reduced. Constructed wetlands are a very small part of the surface water.
Im a BM wrote:
Coastal wetlands are a net source of acidity to the sea if they are drained, which most of them have been, because it allows oxygen to interact with pyrite.

A wetland is not drained. It is a wetland.


The Parrot Killer

Debunked in my sig. - tmiddles

Google keeps track of paranoid talk and i'm not on their list. I've been evaluated and certified. - keepit

nuclear powered ships do not require nuclear fuel. - Swan

While it is true that fossils do not burn it is also true that fossil fuels burn very well - Swan
RE: farms below sea level - drained coastal wetlands29-05-2023 09:11
Im a BM
★★★☆☆
(595)
Coastal wetlands, such as the Sacramento-San Joaquin delta, have been drained for agriculture throughout the world.

In the natural waterlogged wetland condition, low oxygen conditions are created in the soil. This seriously impedes aerobic decomposition, and dead organic matter piles up, year after year. Land surface elevation rises, if anything, and the weight of dead peat pushes it back down. Hundreds of feet thick below the ground surface.

In the drained condition, soil organic matter decomposes at a rate 10-50 times greater than photosynthesis could possible replace via carbon sequestration.

Land surface elevation subsides, year after year, until it is actually below sea level.

The only reason it doesn't fill back up with water is because pumps constantly remove water from the drainage ditches, sending it uphill back into the river.

Far and away the greatest source of sulfuric acid entering surface waters is from these drained wetlands, as they develop "acid sulfate" soils.

Acid mine drainage is tiny by comparison, but provides a nice model because constructed wetlands so effectively neutralize it.

In the wetland condition, microbial sulfate reduction generated pyrite and alkalinity.

In the drained condition, microbial pyrite oxidation generates sulfuric acid and acid sulfate soil of very low pH.

As a brief intro to the hydraulic gradient concept, consider the farmland that everyone can agree is below sea level.

In the Netherlands, they didn't just drain the coastal wetlands, they expanded the farmland out into areas that were shallow sea.

On one side of the dikes is the sea, poised at a higher elevation than the farmland on the other side.

And then there all those beautiful windmills. Constantly pumping water from drainage ditches in the farmland, pushing it uphill and out into the sea.

The farmland is below sea level. The drainage ditches are even farther below sea level. Far enough below to prevent the ground water table from rising up into the rooting zone.

There is a steep hydraulic gradient between the sea level and the farmland, and subsurface flow from the sea constantly pushes in.

The dikes might never break, but if the pumps shut off for too long, the farmland will be flooded.

Technically, they stop being wetlands once they are drained. But they can easily become wetlands again if the drainage water stops being pumped out every day.
29-05-2023 19:48
Into the NightProfile picture★★★★★
(21490)
Im a BM wrote:
Coastal wetlands, such as the Sacramento-San Joaquin delta, have been drained for agriculture throughout the world.

Not a coastal wetland, although it is exposed to the tides in the Bay area.
Im a BM wrote:
...deleted extensive jabberwocky...
As a brief intro to the hydraulic gradient concept, consider the farmland that everyone can agree is below sea level.
...deleted extensive unrelated material...

So? Apparently you would rather destroy these farms and return the land to the useless swamp it was.


The Parrot Killer

Debunked in my sig. - tmiddles

Google keeps track of paranoid talk and i'm not on their list. I've been evaluated and certified. - keepit

nuclear powered ships do not require nuclear fuel. - Swan

While it is true that fossils do not burn it is also true that fossil fuels burn very well - Swan
06-06-2023 21:52
sealover
★★★★☆
(1234)
[quote]sealover wrote:
Submarine groundwater discharge from coastal wetlands is the major source of alkalinity for many marine ecosystems.

In the low-oxygen, organic carbon-rich wetland sediment, bacteria use sulfate as oxidant to acquire energy from organic carbon. Sulfate reduction by bacteria generates alkalinity, rather than carbon dioxide, as the oxidized (inorganic) carbon product.

Three different approaches are offered to engineer coastal wetlands to increase their output of alkalinity to neutralize ocean acidification.

As only one file can be attached, let's start with a good one.
06-06-2023 21:53
sealover
★★★★☆
(1234)
[quote]sealover wrote:
When coastal wetlands are drained for agriculture, buried pyrite is exposed to oxygen. Aerobic oxidation of pyrite by bacteria generates sulfuric acid. In the undisturbed state, the wetland was a source of alkalinity for the sea. After being drained, the wetland exports acidity.

This sulfuric acid input is above and beyond the carbonic acid input from carbon dioxide that is responsible for depleting the ocean's alkalinity. Improved management can dramatically reduce the export of acidity, salinity, and dissolved organic matter from coastal wetlands.

I'll see if anyone is interested in the discussion before I post any more
06-06-2023 21:53
sealover
★★★★☆
(1234)
[quote]sealover wrote:
one more attempt to attach a file

The ocean absorbs more than a third of our carbon dioxide emissions.

The ocean's alkalinity has been depleted ("acidification").

The balance of the sea's carbonate buffer system has shifted.

Carbonic acid is now more abundant, and carbonate ion is relatively more scarce.

Deficiency of carbonate impedes shell formation in marine life.

Commercial aquaculture must now artificially add alkalinity to raise healthy stocks.

Let's see if it let me attach the pdf file
06-06-2023 21:55
sealover
★★★★☆
(1234)
sealover wrote:
Into the Night wrote:
[quote]sealover wrote:
When coastal wetlands are drained for agriculture, buried pyrite is exposed to oxygen. Aerobic oxidation of pyrite by bacteria generates sulfuric acid. In the undisturbed state, the wetland was a source of alkalinity for the sea. After being drained, the wetland exports acidity.

This sulfuric acid input is above and beyond the carbonic acid input from carbon dioxide that is responsible for depleting the ocean's alkalinity. Improved management can dramatically reduce the export of acidity, salinity, and dissolved organic matter from coastal wetlands.

I'll see if anyone is interested in the discussion before I post any more.


Coastal wetlands aren't drained for agriculture. They are swamps. There is nowhere for water to drain to (except a slow flow to the sea, eventually).

If you remove the vegetation from a swamp, it will return in just a few years. That's why it's not used for agriculture. It's too wet and too useless to plant anything (a few have tried rice, but with limited success).

One other swamp crop is balsa wood. This stuff can be 'farmed', and it's light enough you can almost just haul off with a whole tree like Paul Bunyan.

The amount of sulfur that actually becomes sulfuric acid is really very tiny. It can be a LOT more and still not make any significant change in the pH of oceans. You are ignoring a concept in chemistry called 'buffering'. You should probably spend more time learning the chemistry of acid-base reactions.

So you are making a mountain out of a molehill.


Coastal wetlands include river deltas.

The Nile delta was just a "swamp" until people drained it for agriculture.

The Ganges delta, the Mekong delta, etc. are among the world's most productive agricultural land, supporting dense populations.

The amount of sulfur oxidized to sulfuric acid is ENORMOUS. Literally gigatons of buried pyrite in drained wetland soils was oxidized to sulfuric acid as they formed what are known as "acid sulfate" soils.

Right now, the biggest crop for which more coastal wetland is being drained is oil palm. Once the waterlogged peat is exposed to oxygen, the carbon dioxide emissions from these areas rivals that of fossil fuel combustion. Rather than discharge alkalinity in groundwater flows, these areas export sulfuric-acid-enriched surface water to the sea.

The concept of "buffering" is an important one.

If I take a liter of pure water and add just one drop of concentrated acid, I will see a huge drop in pH. If I add a drop of acid to sea water, the pH will hardly budge.

Remember, this thread is about restoring "alkalinity" to the sea.

Alkalinity is another word for acid neutralizing capacity.

The alkalinity of pure water arises entirely from hydroxide ions.

The overwhelming majority of the alkalinity in sea water arises from bicarbonate and carbonate ions.

In the carbonate system, a tiny fraction of the dissolved carbon dioxide is present at any moment in the form of carbonic acid.

Carbonic acid is in equilibrium with dissolved carbonate and bicarbonate ions.

A 30% depletion of the ocean's alkalinity has resulted in only a small decrease in pH.

On the other hand, it has caused a HUGE change to the bioavailability of carbonate ion.
06-06-2023 21:56
sealover
★★★★☆
(1234)
sealover wrote:
The balance of the sea's carbonate buffer system has shifted.

There is no such thing. Learn what 'buffering' means in chemistry.
sealover wrote:
Carbonic acid is now more abundant, and carbonate ion is relatively more scarce.

More made up shit. Carbonic acid forms anywhere there is dissolved CO2 in water. Carbonic acid also forms dissolved CO2 in water. The two reactions form an equilibrium, with only a very small percentage existing as carbonic acid at any given time.

Again, you ignore the concept of buffering in chemistry.[/quote]

You are actually right about one thing. Carbonic acid forms anywhere there is dissolved CO2 in water, and only a very small percentage of dissolved CO2 is present as carbonic acid. But there are certainly more than two reactions.

Carbonic acid is in equilbrium with bicarbonate ion. Bicarbonate is in equilibrium with carbonate ion. There is much, much more bicarbonate than carbonate in sea water.

The third most important contributor to alkalinity in sea water, after bicarbonate and carbon ions, is ORGANIC alkalinity.

Organic alkalinity is the acid neutralizing capacity that arises from anions of deprotonated organic acids.

About one fourth of the alkalinity in submarine groundwater discharge from coastal wetlands is ORGANIC alkalinity.

This matters a lot to marine ecology.

For example, iron is only bioavailable in sea water because it is chelated by organic alkalinity. Ferric iron does not precipitate upon contact with oxyanions, despite sea water pH, because its reactive sites are occluded by organic ligands.

Ferrous iron is plenty soluble in sea water, but easily oxidized by bacteria to the far less soluble ferric form. Complexation of ferrous iron with organic alkalinity protects it from oxidation, because its reactive sites are occluded by organic ligands.

Organically-complexed iron in submarine groundwater discharge is what allows many marine ecosystems to grow at all.
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