This letter to Dr. Richard A. Feely of NOAA’s Pacific Marine Environment Laboratory Carbon Program in Seattle, WA was sent by Chuck F. Wiese on Wednesday. Chuck also asked me to post it on WUWT but I wanted to see if NOAA would fix the error on the web page first. It is now Saturday, and they haven’t, so I think a public notice is appropriate. I suppose I’m not surprised though, since Dr. Feely lists “Nobel Peace Prize (co-shared with Al Gore and other members of IPCC) – 2007” on his web page. I suppose anyone who lists Al Gore along with the gross errors he makes, such as his laughably non-reproducible “high school physics” of CO2, would not bother to correct their own gross errors. – Anthony
==============================================================
Dear Dr. Feely:
I exchanged e-mails with you a while back over a story that ran in the Oregonian on April 12, 2012. It was about “ocean acidification” that was supposedly killing off what would otherwise be healthy oyster harvests here in the Northwest, The story can be found here:
An OSU researcher who gave the story to the Oregonian, Alan Barton, had incorrectly asserted that the ocean pH had risen 30% because of human CO2 emissions and gave that as the reason the oyster harvests had been suffering. And he qualified that statement by stating that the ocean pH had moved .1 unit towards acidity over the last century.
But as you know, the equation for the pH of an aqueous solution is logarithmic and defined as pH = -log[ H+ ] . As you also know, there are 14 orders of magnitude that define the pH scale from zero to fourteen units as per this equation. So a movement of .1 units towards acidity cannot equal a 30% increase in acidity as claimed in this article. It is actually .1/14 or only 7/10ths of 1%. In order for there to be the increase cited, the researchers solved it for the hydrogen ion concentration and computed that change instead and called it the change in acidity. So if we moved .1 units towards acidity from the alkaline 8.2 to 8.1 oceans and compared the change, we have [delta H+] = 8 E-9/6 E-9 = 1.33 or a 33% increase in the hydrogen ion concentration, not an increase of 33% in the pH. None the less, that is how the story was reported and it is wrong.
Since the natural variation of ocean pH can be up to 5% in either direction, I am speculating that in order to make the story seem legitimate, a gross exaggeration of fact was needed to sell it and hence the switch and bait tactic was used with the pH equation.
You agreed with me in my premise that hydrogen ion concentration makes up the pH but it is not defined by that number because the number of ions in an aqueous solution of water are very large. That was the whole idea behind creating a logarithmic scale with the 14 orders of magnitude to define it. I reported this to the Oregonian readership and thought the issue was settled. But then I found this:
http://www.pmel.noaa.gov/co2/story/What+is+Ocean+Acidification%3F
In this explanation offered by NOAA, of which you are a senior scientist, we are back to the trickery of claiming the ocean acidity has increased by 30%. Are you aware of this NOAA information page? It needs an immediate correction. The ocean pH has been changing everywhere within natural variations. There is no provable decrease that can be identified with atmospheric CO2 that is related to human activity. Does Jane Lubchenco understand this? She has made numerous and completely false assertions that the up welling ocean water off of the Northwest coasts ( that will be on the rise because of the switch to cold phase PDO in 2007 that will run thirty years and likely decrease the pH additionally ) is attributable to human caused climate change. There is absolutely no proof of this and as far as meteorologists can tell, the mid and north Pacific Hadley cell summer circulation has intensified on schedule and is behaving perfectly normally in the cold phase of this ocean cycle. Either you or Lubchenco need to correct this page. It is misleading the public.
Sincerely,
Chuck F. Wiese
Meteorologist
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“””””…..E.M.Smith says:
June 30, 2012 at 1:51 pm
Shell fish don’t have a problem with acid water anyway:
http://chiefio.wordpress.com/2012/03/08/clams-do-fine-in-acid-water/.
Fresh water clams are an existence proof that acid water ( up to 4.x pH) does not harm them…..”””””
I am somewhat of an expert on fresh water clams, and their effectiveness in growing in acid water; to wit, the California Sacramento/San Joachin/Mokelume Rivers Delta system.
A few years ago, while fly fishing for striped bass with my son, in a secret location, in Frank’s Tract, I actually made a total of 25 casts, for a total of 24 grabs with 24 successful landings, and live releases, with an unbroken string of 21 grabs and hookups in 21 successive casts.
Heck no they weren’t striped bass, they were fresh water clams. Every one of them had the pointy end of my fly in its mouth; excuse me, shell ! I guess the bed of clams were just sitting there on the bottom, open to catch food coming by in the current, and every one of them grabbed my fly, as it brushed over them. The clams were about one inch diameter, and the fly was about four inches long. For the record, it was a chartreuse and white Clouser, tied on a 3-0 hook. Every one had it’s shell closed on the hook point; which evidently is the tasty part of a Clouser. Yes I did feel the grab, and set the hook on them, but none suffered any damage.
It’s still a secret location, because my son and I have never been able to find that clam bed again; maybe I scared them all off to some other place.
Willis Eschenbach says:
June 30, 2012 at 11:22 pm
I have three problems with the statement about a “30% increase in pH”. First, we have no observations saying it has changed that much, just claims without actual data to support them.
Willis, I fully agree that a “30% increase in acidity” is an absurd claim and only intended to scare people with large sounding figures. For coastal waters, indeed the pH differences are far more variable and have no influence on fish or corals or clam shells…
But there are a few longer term observations which show that there is a small decrease in pH in non-coastal ocean waters, be it that the pH is not directly measured, but calculated from DIC and alkalinity changes. See:
http://www.bios.edu/Labs/co2lab/research/IntDecVar_OCC.html
Instead of arguing about what pH actually means and whether the oceans are turning to HCl /H2CO3or not let us look at the actual observations of ocean surface water pH.
Whilst not measured everywhere, ocean pH has been found to vary, daily, seasonally and cycically over longer periods, from pH7,4 to pH 8,3. All reported reductions have fallen within this bracket. Water issuing from the deep ocean black smokers, volcanic vents on the ocean ridge system, have a pH of 4.5 or lower but this rapidly increases the further away from the vent the pH is measured. There is a buffer stage at work in the ocean water, the bicarbonate buffer. This is the next stage in the solution of CO2 in the sea water the first stage being the formation of carbonate ion from the CO2/H2O. This bicarbonate stage increases the pH and is continuous. Remember that sea water is an ionic solution not a simple mixture of chemicals so the identification of H+ in it is no surprise.
It is the bicarbonate ions that molluscs etc use in the formation of shell or skeletal frames. During the early Ordovician CO2 levels were up to 8000ppmv but the ocean pH was similar to today’s and molluscs and corals thrived probably due to the excess bicarbonate building blocks reduced energy required to grow shell to divert energy to grow larger.
Phew! Weren’t they lucky to have chosen the H+ ion concentration as reference, and not the OH- (OH minus) ion concentration?
Remember that in water the two are firmly related – multiplying the two concentrations gives 10E-14. At a neutral pH of 7 both are 10E-7, and at pH of 8.2 the H+ concentration is 10E-8.2, while the OH- concentration becomes 10E-5.8.
So, if the water were ‘acidifying’ from pH8.2 down to neutral at pH7.0, some 94% of all OH- ions were already lost, and many would say that pretty much all of OH- is lost already, losing only 6% more cannot possibly have any effect. Therefore it almost couldn’t get any more acidic than that? No catastrophe, everything is safe at this point? Imagine what poor message this would have sent!
The flaw in thinking is the ignorance about biological/chemical/physical effects being governed by what is correctly measured by pH, namely the electrochemical potential, as the first commenter has already pointed out.
All of the above have an error. pH is NOT described by concentration. It is described by activity. Activity is related to concentration through factors such as as total ionic strength (for dissolved ionic species), the presence of biota, dissolving-but-not-dissolved species, precipitates, colloidal sized solids … all these affect the relation between concentration and activity some in ways that cannot be accounted for with accuracy. A change of 0.1 pH units can be due to the physical properties of a pH electrode, if one is used, or from the abovementioned factors in calculations based on stability constants/phase diagrams. A change of 0.1 pH is in the expected error envelope with seawater – next to nothing. You are all wrong, wrong, wrong.
Were you not taught Debye–Hückel theory in first year Chemistry?
Geoff, of course activities are the quantities that matter, but at these concentrations of hydrogen ion, it won’t matter if one uses concentrations or activities to calculate the relative increase in [H+] from the given change in pH.
The Debye-Huckel theory, even extended, breaks down at concentrations > 0.1 m. With an ionic strength of 0.7, seawater is outside the realm of normal activity theory and any measurements of pH have to be done empirically-hence the modified pH measurements and revised buffer standards made from artificial seawater discussed above. Assuming that the current average of 8,1 for seawater pH is based on a corrected measurement, how could the measurement from the beginning of the Industrial Age have any meaning in this context when it was made long before theory and accurate measurement were available.
To become acidic the hydrogen ion content of the sea water offshore from Oregon would have to increase 6121% more than the 26% (not 30%) change. The measurement was over a one century period.
This means that 6121 years from now the ocean near Oregon will become acidic.
It is hard to really generate a sense of immediacy or panic for a time period greater than the written history of mankind.
Dan Johnston says- “…how could the measurement from the beginning of the Industrial Age have any meaning…”
Indeed. The 0.1 pH drop has no meaning because it is not based on measurements.
Dennis Ambler posted an article at SPPI on April 27, 2010-
“The decrease of 0.1 from the “pre-industrial” figure is an average of a calculation from an
estimate, as quoted in AR4 WG1: “A decrease in surface pH of 0.1 over the global ocean was calculated from the estimated uptake of anthropogenic carbon between 1750 and 1994 (Sabine et al., 2004b; Raven et al., 2005)”
“The mean pH of surface waters ranges between 7.9 and 8.3 in the open ocean, so
the ocean remains alkaline (pH > 7) even after these decreases.”
So, the centennial 0.1 pH reduction is computer model garbage, regardless of the units.
We don’t even have adequate measurements of the average global pH of the oceans TODAY!
Jane Lubchenko is no dummy, though. She is responsible for increasing NOAA’s budget as much as possible. She requires misleading or alarmist claims to compete with NASA GISS.
Here are some quotes from the website of Prof J. Timothy Wootton, who is very alarmed about ocean acidification-
http://woottonlab.uchicago.edu/index/global-change/global-change-impacts-on-ecological-networks
“Hence, predictions have been made that ocean pH will decline with increasing atmospheric CO2 emissions, and that this decline will be sufficient to disrupt major physiological processes such as calcification. While the physics of this reaction are well known, there are surprisingly few published data of measurements of pH change in the ocean through time.”
“Even over the course of a day, pH typically varies by 0.24 units, a consequence of the uptake and production of CO2 through photosynthesis and respiration. Hence biological processes, which are often left out of models of ocean pH, can have strong effects. Over the entire span of the data, ocean pH is clearly declining as atmospheric CO2 increases, but at a rate an order of magnitude faster than predicted by current physical models.”
In other words, after spending 10 years taking pH measurements at one coastal location (Tatoosh Island, Washington), they have no idea what is going on with ocean pH.
Mitch says:
June 30, 2012 at 12:56 pm
Gary Pearse: An increase in pH is a decrease in H+ concentration
pH = 7 –> [H+] = 10^-7
pH = 8 –> [H+] = 10^-8
The rest of my comment dealt with an increase in hydrogen (I suppose Hydronium is more correct these days) ion concentration and I slipped up in one sentence – you are correct, of course. My main point was that to go from pH8.2 to pH1.0 required an increase in [H+] of 1,584,893,200%. I was startled that a chem prof of all people would not understand the delta pH significance.
Chem Prof seems to have misunderstood the nature of the complaint. The ion concentration is not the acidity (or alkalinity) as munderstood in pH. It is not used to derive the pH from -log10 of H+ ions.
The measurements of the ocean are of pH.
The ion concentration is derived from the pH. Not the other way round.
And the pH is not that accurate. +/-5% (calibration slope of 95%) is the industry norm; all the buffering standards assume that.
So 30% change in ion concentration is less than the calibration error that derives the measurement of pH at the pH of the ocean.
The complaint is right. NOAA is not just misleading, it is wrong.
How about the impacts of run off / effluent from nearby land areas?
Last week I posted a comment and links here to a couple of stories in the Seattle Times about the impacts of “acidification” on Willapa Bay oysters. I emailed the reporter with the following questions:
Craig,
In reading your article a couple of questions arose.
1) Can the researchers studying the “acidification” issue distinguish between CO2 from deep ocean upwellings and that from the atmosphere?
2) Since increasing atmospheric CO2 is a global phenomenon, why is the pH change from it occurring faster in Washington than in Hawaii?
3) Is anyone taking regular pH measurements for Willapa Bay and if so, with what periodicity?
He responded back right away. Unfortunately his responses were not that helpful. To my first question he provided a link to a story that said nothing about identifying the source of CO2. To the second he referred me to the part of his story saying that it had to do with how upwellings hit the NW coast. I could tell from his response that the possibility never occured to him that the increase could be primarily these currents. After a followup email to him, he referred me to Dr. Feeley. I’ve been debating whether or not it is worth my time to contact him.
I get the feeling that the press and perhaps a good number of researchers do not understand the importance of wanting to sift the wheat from the chaff. When nearly everything gets tied back to climate change these days, how is the average citizen supposed to figure out what is a real problem needing to be addressed and what is simply speculation.
This is not about politics. It is about arithmetic and simple arithmetic functions.
Chuck Weise’s WUWT post says
nothing about sources of error in measurements of pH,
nothing about sources or sinks of hydrogen ions in ocean brine,
nothing about complex equlibria,
nothing about the effects on hydrogen ion concentration due to other species,
nothing about non-ideal behavior of hydrogen ion in solution.
Here are things that he actually wrote:
(1) “As you also know, there are 14 orders of magnitude that define the pH scale from
zero to fourteen units as per this equation. ”
This is incorrect. The pH scale is open-ended.
(2) So if we moved .1 units towards acidity from the alkaline 8.2 to 8.1 oceans and
compared the change, we have [delta H+] = 8 E-9/6 E-9 = 1.33 or a 33% increase
in the hydrogen ion concentration, not an increase of 33% in the pH. None the less,
that is how the story was reported and it is wrong.
In fact, the story does not mention pH at all. Lori Tobias quotes Alan Barton
(hatchery research manager at Whiskey Creek Shellfish Hatchery on Netarts Bay), ‘
“Over the last 100 years we’ve made the ocean a little more acidic than it used to be,”
he said. “There is a 30 percent increase in the acidity of the ocean. If you are an
oyster lover, that little bit more acid is a big problem. Eventually it will put our
hatchery out of business.” ‘
No mention of pH.
Here is a list of every reference to acids, acidification, or acidity in the article:
“Rising levels of carbon dioxide — which lead to increased acidity in the ocean
water, or ocean acidification — were making it difficult, if not impossible, for the
larvae to grow.”
“The shell [of oyster larvae] is easy to dissolve and sensitive to acidic conditions,
Barton said, unlike the hard adult oyster shell that’s made of calcite.”
“Some say it is impossible for the larvae to grow the shell; some say they can, but
it is really hard to do.They use a lot of energy and don’t grow. Whether it is
impossible or just difficult, they are still dead. We know that the ocean acidification
is causing our problem.”
“The impact of ocean acidification is heightened by upwelling, which occurs when
winds blowing from the north push the ocean surface waters away from the coastline,
allowing deeper waters to move to the top. The deeper waters are already higher
in carbon dioxide from all the decomposition below. Water that upwells is always
higher in acidity, but our use of fossil fuels has added to the carbon dioxide in
the atmosphere, in turn increasing ocean acidity, Barton said. ”
“Over the last 100 years we’ve made the ocean a little more acidic than it used to
be,” he said. “There is a 30 percent increase in the acidity of the ocean. If you are an
oyster lover, that little bit more acid is a big problem. Eventually it will put our
hatchery out of business.”
That is it. No mention of pH.
(3) “You agreed with me in my premise that hydrogen ion concentration makes
up the pH but it is not defined by that number because the number of ions in an
aqueous solution of water are very large. ”
This is incorrect. Chuck Weise is correct earlier when he says that pH is defined by the
equation pH = – Log[H+], where [H+] is the hydrogen ion concentration. Now he says
it isn’t defined ‘by that number.’ This is just wrong. In fact, pOH and pK, and for that
matter, pAnything are defined in a similar manner:
pAnything = -Log(Anything)
with the corresponding unique inverse relationship
Anything=10^(-pAnything) .
This is done in chemistry all the time because the scale of these quantities vary by many
orders of magnitude.
How do chemists describe how much of a given substance is present in a solution?
There are a number of ways, but every single one of them can be related to the molar
concentration of a substance, that is, moles of substance per liter of solution, which is
usually written as [X], where X is the substance in solution; It links two quantities:
(a) the moles of a given material – a specific way of counting the molecules or ions
of a given type and (b) the volume of the solution measured in liters.
For example, hydrogen ion concentration, written [H+], represents the moles of
hydrogen ion in a liter of solution.
What does Chuck Weise man by “the number of ions in an aqueous solution of
water are very large” ? I have no idea and it is irrelevant.
Comments that argue that “It’s even more complicated than that, because there are
buffers involved” or something like that are missing the whole point of the acid-base chemistry
of a buffered. The presence of a buffer (another weak acid or base) in significant quantity
makes it more difficult to change the pH of a solution, not easier. So a signficant decrease
in the pH of a buffered solution is a clear indication that a significant source of acid has
been added.
Some comments represent serious scientific ignorance:
“It is being assumed by these people that the ocean obeys the second law of thermodynamics,
it does not because of surface tension.”
“The oceans are infinitely buffered.”
“A pH change of .1 corresponds to a change in hydrogen ion concentration of ..007%.”
“A pH change from 8.2 to 8.1 cannot be truthfully described as ‘becoming ‘more acidic’. ”
“the acidity isn’t increasing; the alkalinity is decreasing.”
“pH is (negative) log because that is how organisms perceive acidity. They don’t perceive
it in a linear scale, so it shouldn’t be quoted in one. No-one, but no-one talks about acidity
other than via pH.”
“The reason the change in pH is meaningless in this situation is that in a pure system where
only H+ is considered to be driving pH, the change is one gram of hydrogen ions in one
billion liters of water.”
“Weren’t they lucky to have chosen the H+ ion concentration as reference, and not
the OH- (OH minus) ion concentration?”
“Chem Prof seems to have misunderstood the nature of the complaint. The ion
concentration is not the acidity (or alkalinity) as munderstood in pH. It is not used to
derive the pH from -log10 of H+ ions…The measurements of the ocean are of pH…
The ion concentration is derived from the pH. Not the other way round.”
“As a Chemical Professor – cough! – you will be aware that there is a p[OH] measure too.
So why not quote the alarming story that – oh noes! – hydroxide concentration in the
oceans has fallen by 80%. I would hope you would see how stupid it was to use it,
regardless of being technically true.”
NOTE: That isn’t true; a 0.1 decrease in pH corresponds to a 0.1 increase in pOH, with a
corresponding decrease in [OH-] of 20.6%. If you are mystified by this, please note this
arithemetic: 1.26 x 0.794 = 1.00 .
Please note: “I’ve copied a discussion from Wikipedia…” is not the strongest line of
argument one might take.
Quite a few comments indicate there is confusion between the ideas of variablity in a
measurement and an error in a measurement. There is a large variability in the height of
a human, varying from 0.55 m tall Chandra Bahadur Dangi of Nepal to 2.45 m tall
Zeng Jinlian of the People’s Republic of China. This natural variation does not preclude
us from measuring individual height to a precision of 0.001 m or better. And variations
in human height are worthy of study:
Chao-Qiang Lai, of the Jean Mayer Institue wrote
‘ …”How much variation (difference between individuals)
in height is attributable to genetic effects and how much to nutritional effects?”
The short answer to this question is that about 60 to 80 percent of the difference
in height between individuals is determined by genetic factors, whereas 20 to 40
percent can be attributed to environmental effects, mainly nutrition.’
http://www.scientificamerican.com/article.cfm?id=how-much-of-human-height
He also writes
Heritability allows us to examine how genetics directly impact an individual’s height.
For example, a population of white men has a heritability of 80 percent and an average
height of 178 centimeters (roughly five feet, 10 inches). If we meet a white man in the
street who is 183 cm (six feet) tall, the heritability tells us what fraction of his extra
height is caused by genetic variants and what fraction is due to his environment
(dietary habit and lifestyle). The man is five centimeters taller than the average.
Thus, 80 percent of the extra five centimeters, or four centimeters, is due to genetic
variants, whereas one centimeter is due to environmental effects, such as nutrition.
Notice that one is still able to make a strong scientific statement about a 1 cm height difference
in spite of a 200 cm wide variation in human height.
Some commenters hang their hats on the high ionic strength of sea water (it is signficant,
about 0.73 mole/liter) or the difference between the activity of hydrogen ions and [H+], but
entirely forget that the activity of a 10^(-8) molar solution is —- 10^(-8) molar ! Debye-Huckel
theory plays no role in this whatsoever.
Chuck Weise adds, “In all of the work- ups and computations I have seen NOAA and
others do when talking about ocean acidity, the units have always been referenced in
units of pH. I have never seen work- ups in ion concentration” and misses the point again.
Some comments are rich with irony:
“Does anyone know how much CO2 it would take to change 1.3 billion cubic
kilometres of [buffered – my clarification] salt water from pH 8.2 to 8.1?”
“Because even though the numbers do calculate to roughly 30%, it’s incredibly
inappropriate to apply percentages with pH.”
“To many non-scientific readers this implies a hugely significant increase in
environmental impacts – 30% more acidic ! NOAA compound the misleading nature
of this statement by not making it clear that this is a reference to a percentage
change in hydrogen ion concentrations.”
Willis Eschenbach:…”applying percentages to logarithmic scales doesn’t work.”
Exactly.
Chem Prof says:
“Some comments are rich with irony:”
Exactly.
Let me some this up with an analogy: Let’s say you’re a company being accused of paying “slave wages”; but you state that you’ve increased wages by 30%. A 30% increase is meaningless without knowing 30% of what. If you’ve increased wages from a penny an hour by 30% that’s still “slave wages”. The press release similarly misleads the average person because they may not know what the total is the 30% is in reference to. It’s unethical zohneristic advocacy, not objective science. But any chem prof would know that it is incredibly inappropriate to apply percentages to pH’s instead of thinking that is somehow ironic.
BTW: Chem Prof, I’m doubling … nay, tripling the money I’m paying you to post here.