WUWT reader Peter Gadiel writes:
After reading of the critique of Sabine’s exclusion of the historical data on ocean acidification I emailed him. I thought his response might be of interest to you at WUWT. He says the earlier data is not of “sufficient quality.”
My question to him:
As a taxpayer who is helping to pay your salary I’d like to know why you are refusing to include all the data on ocean acidification that is available.
Sabine’s response:
Chris Sabine – NOAA Federal
12:31 AM (11 hours ago)
As a public servant that must stick to the rigor of the scientific method and only present data that is of sufficient quality to address the question, I am obliged to report the best evaluation of ocean chemistry changes available. This is what you pay me to do and I am working very hard to give you the best value for your tax dollar every day. I hope you are having a good holiday season.
The question that immediately comes to mind is:
Who determined that the directly measured ocean pH data was not of “sufficient quality” and if it wasn’t, why then did NOAA make the data available on their website as part of other ocean data in their World Ocean Database without a caveat?
My search on NOAA’s NODC database for ocean pH data showed plenty of data and no caveats on use:
So was Sabine’s decision arbitrary and without basis in fact? Inquiring minds want to know.
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“I am obliged to report the best evaluation of ocean chemistry changes available.”
—
Sabine prepended modeled ocean PH values to the observed values to hide the decline in observed PH readings prior to 1985. How is that different from what Michael Mann did with his hockey stick when he appended observed temperature records to his tree-ring temperatures to get the desired results?
Who determines what “evaluation of ocean chemistry changes” is the best. And what accepted scientific standard is used to make that determination? The PH chart shows a drop in PH for about 15 years after 1985, then it rises for about 10 years before dropping again. That does not follow the steady rise in CO2 over the same time period. So, how can they even assume to estimate the PH of the oceans prior to 1985 if they don’t understand what caused the fluctuations in PH after 1985? Ocean temperatures have cycles. ENSO has cycles. So, why wouldn’t ocean PH values have cycles. Periodic upwelling of deep ocean water could have an effect on PH, just like it does on ocean surface temperatures. It seems to me that less than 30 years of ocean PH data is not long enough to account for possible cycles in ocean PH that could be longer than 30 years.
+1
Sorry Louis,
Sabine used real far more precise measurements for the period after 1984, here for Bermuda(fig 5):
http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
That is what the red line in Wallace’s graph shows after 1984: a drop of 0.04 pH unit.
The red line before 1984 is the theoretical pH for the amount of extra CO2 dissolved in the ocean’s surface.
The faint blue line is the pH drop of 0.3 units according to glass electrode pH measurements. But these are simply unreliable due to measurement error and sampling. There is no such a dip and recovery and dip again in the period since 1984, only a steady decline in ratio to the CO2 increase in the atmosphere.
Ocean cycles (temperature) have little influence in this case…
a drop of 0.04 pH unit. and the error margins are what ?
Its become far to common to see claims of high levels of precision being made when in fact the actual ability to measure to these levels simple is not there .
Ocean cycles (temperature) have little influence in this case
==============
you have way too little data to establish that.
knr, the precision of the colorimetric pH measurements approaches 0.001 pH unit:
http://www.sciencedirect.com/science/article/pii/S0003267013006570 and several others.
They are developing micro pH measurements now for maintenance free underway measurements on commercial ships, as is already done for pCO2 measurements.
ferdberple,
The main influence from ocean cycles (including ENSO) is temperature and the related change in biolife. Both influence the pCO2 and pH over the seasons and on longer term for temperature trends.
In Bermuda, the seasonal variability is twice the variability in Hawaii:
http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
Temperature change over the seasons: average 8°C
pH change over the seasons: average 0.09 pH unit
DIC change over the seasons: average 1.5% due to increased biolife
pCO2 increases from 320 to 400 μatm in summer mainly from increased temperature, minus DIC decrease.
Any change from ocean currents is in the order of less than 1°C, should have an influence of about 0.01 pH unit.
Something similar for Hawaii:
http://www.pnas.org/content/106/30/12235.full.pdf
3°C change over the seasons
0.03 pH unit change over the seasons
40 μatm pCO2 change over the seasons
There are fewer than 500 measurements *in total* at Bermuda.
That’s fewer than I’d take in a year in my back garden for max/min temperature.
Would it be reasonable to extrapolate from my readings to infer global trends? If so I predict that we’ll see powerful warming for the next six months……..
Here I stand, hat in hand, a humble taxpayer who depends on your superior expertise, sir. Is it true that the oceans are becoming less caustic?
“Sabine’s excuse for using modeled data over real data?
There is no such thing as “modeled data”. Model outputs are not data.
Sabine didn’t use modeled data, he used the best measured data available since 1984. Wallace used glass electrode pH data which have wide margins of error…
But we all know there is such a thing as a “modeled guess”. The problem enters in when the “guess” is treated as an observation and the observation dismissed because it diverges from the “guess”.
It’s quite possible that what he means is that historical measurements don’t fit with the theoretical calculations and therefore are immediately suspect. I’ve seen quite a few scientists get confused this way. The other alternative is, of course, that the theoretical calculations fail to take into account all of the factors affecting pH. This is just a lengthy way of saying that if the measurements don’t fit the model then the measurements must be wrong.
Goldie, it is the other way out:
The theoretical measurements fit widely within the bad performing pH measurements. Even in the period since 1984, the real pH drop by the better (not modeled) measurements give a drop of 0.04 pH unit, while the glass electrode measurements show a drop of 0.3 pH unit. Thus Wallace is wrong to accuse Feely and Sabine of omitting valuable measurements of the past, as the GE measurements have no value at all.
so what was the magic event in 84 that suddenly made poor measurement good?
And what affect does included rather excluding these ‘poor’ measurements .
But in one way your right there simple is not enough measurement to give a Value for ocean pH worth a dam and there never has been , the trouble is ‘models ‘ cannot create them either not matter how well those models give you the results ‘you want ‘
Why wouldn’t the 80 years of GE measurements have value on what was occurring during and over the 80 year span of GE measurements?
Why didn’t Sabine ponder and report his assessment of all those years?
Why do defenders of such cherry picking omission insist on obfuscating for Sabine?
These are the chronic cherry picking alarmists who scold skeptics for cherry picking and attribute every weather event to AGW while accusing skeptics of confusing weather with climate.
And so on……
Using Feely’s model, what was the pH of the oceans when CO2 was 280 ppm, 185 ppm and 4,700 ppm, 12,000 ppm and let’s say 100,000 ppm in the early Earth?
as the GE measurements have no value at all.
=============
you haven’t established that. I did a sport check on some data from 1910 and they have pH recorded to 1/100’s pf a decimal place, which would appear to demonstrate you really don’t know what you are talking about with regard to accuracy.
8.25
8.23
8.21
8.21
8.14
8.09
8.09
8.12
8.12
Engelbeen,
With all due respect, as the comedian once said, “It’s a small world, but I wouldn’t want to paint it.” You reject 3 million measurements at your peril, as they may have been not sufficiently random nor well enough distributed? Well were they or were they not?
You are up on your high horse, American expression, but why?
Yes some group may have taken 3 million measurements which are now “Proven” to be useless, but they are not so proven, and who could imagine that they were and are useless?
Reject the data that we DO have, subject yourself to urgent questioning, good luck with all that. Contrarian, fine, but be a better one…
Glass electrodes produce a potential difference in response to cation strength. Glass can be made selective, for H+ etc. But measuring 10^-8M H+ in the presence of 0.4M Na+ is a challenge which was never easy to meet.
knr
so what was the magic event in 84 that suddenly made poor measurement good?
The introduction of colorimetric pH measurements in the begin 80ies, for the first time used in fixed stations. The less performing measurements were still taken, but gradually replaced.
And what affect does included rather excluding these ‘poor’ measurements
A drop of 0.04 pH unit in the period as measured in fixed stations
A drop of 0.3 pH unit as measured by glass electrodes over the same time frame, mainly due to bad sampling.
Measurements at fixed stations in open ocean give a better idea about the pH drop everywhere (as ocean chemistry is the same everywhere in the bulk of the ocean surface), as good as measurements of CO2 at a few fixed stations far away from other influences give a good idea about the increase of CO2 in the atmosphere…
Steve Oregon,
You are accusing the wrong person: Sabine did use the best available data, which are all after 1984. Wallace used unreliable data from a method that can’t show the trend due to accuracy (while more accurate calculated values were available) and lumped all samples together without taking into account place and seasonality. So, who is cherry picking here?
Michael Moon
Sorry, used the wrong reply button. Reply is somewhere down (and under moderation for now)…
ferdberple,
CO2 values at Mauna Loa are published with 2 figures after the decimal point, even if the accuracy of the method is not better than 0.2 ppmv (they publish the average of 1 hour of sampling and they give the stdev of all samples over that hour).
The pH device may give 2 figures after the point, but that doesn’t say anything about the accuracy. Only if they give the calibration figures of repeated measurements, one can have some idea… There were also calculated pH values, based on TA and DIC, these show better repeatability and accuracy. I don’t know if these are clearly distinguished from direct pH measurements.
My very long time (40 years) ago experience with glass electrode pH measurements was that these were not better than 0.1 pH unit. In seawater it seems even far more difficult…
Fernando writes “as ocean chemistry is the same everywhere in the bulk of the ocean surface”
Any chemistry is the same anywhere but that seems irrelevant since pH can be impacted by a great many varying factors so knowing the pH at a few locations and assuming that gives you good global averages capable of measuring trends is poor science imo.
TimTheToolMan,
The impact of more CO2 in the atmosphere can be calculated for every point in the (bulk) oceans, except for huge variability from upwelling and estuaries. That is established chemistry.
If you look at the pH decline over now 7 stations in different places over the oceans: (fig. 7):
http://www.tos.org/oceanography/archive/27-1_bates.pdf
all stations show an increase in DIC (total carbon), pCO2 and a pH decline. All the result of the CO2 increase in the atmosphere…
That is awful reasoning Ferdinand. There is much more going on in the oceans than just CO2 impacting their pH.
Sabine needs to be reminded that as a public servant, his job is to collect and present, not judge. As a scientist, to be 100% impartial, not partisan.
I bet if we gave Sabine money to certify the historical data he’d take take the money even though he’s already concluded it is wrong. Confirmation bias again.
A half decent scientist would:
a) determine which data is reliable enough to be used to support the claims being made.
b) reject the data that does not meet the criteria that is established in a).
c) if the data is unreliable prior to a given date, note this in any conclusions that are drawn from the data.
d) if they decide to use a model to extrapolate into time periods that precedes their reliable data set, they must acknowledge that they are using a model.
e) Recognize that use of a model means that any conclusions that are drawn about the extrapolated time period(s) in question should be taking with a large grain of salt.
Ian, Sabine did exactly what you describe a) to c): he only published the data after 1984 as that were the only data of sufficient quality.
Now he is accused by Wallace of omitting the data pre-1984, while these have no value at all to establish the trend in the period 1850-1984.
That is the same as accusing Dr. Spencer of not using the ground based temperature data in his satellite data…
What was the magical event that made all data before 1984 bad but all data on or after good ?
knr, the development of colorimetric pH measurements instead of glass electrodes and the use of fixed stations besides ship’s surveys. The latter is important to establish the large variations over the seasons, the former to have data which are fine enough to show a trend of 0.05 pH unit over 100+ years…
Before 1984, there were calculated pH measurements, based on other, more accurate measurements (total alkalinity and total carbon). But neither Sabine nor Wallace have used these data…
this question is like asking a natural health therapist why they recommend a super-multivitamin over a regular multivitamin to cure cancer.
the people involved in the field (climate science/environmentalists) are just drifting further away from real science with every paper released.
let them go. if people are not smart enough to understand the problems with the way they conduct their ”science”, then they have no hope of understanding the actual content of the ”science”, so it is pointless pointing out how wrong the ”science” is. they will only see the window dressing (media consensus) and defend that to the death. if it is to be that the world is past its critical thinking phase (enlightenment) completely, then it wont matter how many objections are made.
Good God. Has Sabine never studied Theories of Science? Is it possible that Sabine never understood Mathematic Statistic? The words ‘earlier data is not of “sufficient quality.”‘ is something one would expected from 7th graders, not from anyone who studied beyond College.
Start by reading: Theories of Science, Basic Knowledge
Where has all the money gone, from where did You get it?
Follow the money and what will we find? Something they, the CO2-believer’s leaders, never expected?
+1
To study is one thing – To Study understanding an other. In my view a Scholar who doesn’t show any knowledge regarding Theories of Science – Haven’t studied enough.
“You cannot make a scientific report more accurate by excluding data.”
No, but you damned sure can make it support your crackpot hypothesis by excluding data 😉
And you can make any report worthless by including bad data…
First define what is ‘bad data ‘ ,is it data which likes accuracy , in which case much of climate ‘science’ is filled with bad data or that which is bad because it does not support what your trying to prove.
In this case it is clearly data which aren’t accurate enough to show the trend which you want to look for and under sampling in time and place. You can’t see a (theoretical) trend of 0.05 pH unit where your measurement is accurate to 0.1 pH unit and the spatial and seasonal changes can go up to 1 pH unit difference…
Therefore you need fixed stations to establish sufficient sampling to show the seasonal variations at different places on earth to show the spatial differences…
Re:
“Frank Kotler December 26, 2014 at 2:52 pm
Here I stand, hat in hand, a humble taxpayer who depends on your superior expertise, sir. Is it true that the oceans are becoming less caustic?”
This will be my take away for future discussions with my AGW friends. Well done.
“Riding the global cycles
Diatoms fix as much carbon dioxide as all the rainforests of the world combined, and they may very well have been the main architects of our current, moderately cool climate situation. The rise of the diatoms began in a much warmer climate than ours, with no ice caps on the poles. The atmospheric carbon dioxide concentration was much higher than today. In the Cretaceous, around 100 million years ago, when diatoms began to become widespread and developed great diversity, the carbon dioxide level was fivefold higher than today, and oxygen was lower. Remarkably, diatoms managed to thrive and expand during a period of extreme climate change, and they also seem to have come through the mass extinction that saw off the dinosaurs without too many problems. The opening of the Drake Passage around 40 million years ago, which created the continent of Antarctica, was particularly beneficial for the diatoms because they began to proliferate dramatically in the cold turbulent waters of the Southern Ocean.
As diatoms evolved thicker and denser cell walls and spread across the oceans, it became more likely that dead diatoms might sink to the ocean floor and thus sequester their carbon.”
http://www.sciencedirect.com/science/article/pii/S0960982212008664
“Shells – Carbon Transport Down to the Deep
Shell-building organisms such as coral, oysters, lobsters, pteropods, sea urchins, and some species of phytoplankton use calcium carbonate ions to build their shells, plates and inner skeletons. The carbon that is incorporated into the shells of these organisms can end up in deep ocean sediments as these organisms die and sink. Although some of the shells dissolve before reaching the seafloor sediments, shells slowly build up on the sea floor storing the carbon for millions of years.
Coccolithophores
Coccolithophores[reuse info] Phytoplankton bloom Key of Biscaye france
[reuse info] Coccolithophores perhaps have had the biggest impact on the carbon cycle over time. These microscopic phytoplankton remove carbonate ions and calcium ions from seawater to build their calcium carbonate (CaCO3) plates – called coccoliths. When there is plenty of sunlight and nutrients, these tiny phytoplankton will explosively reproduce, producing a “bloom” of trillions of coccolithophores floating in the surface of the ocean. Satellites can see these blooms from space, such as the very large bloom above that appeared off the coast of Norway in the Barents Sea. In just a few days, coccolithophores gobble up the available nutrients and start to die. The trillions of coccolith plates slowly sink down to the bottom of the ocean taking the calcium carbonate in their plates with them.
The calcium carbonate in these sediments are actually chalk – the same type of chalk used to write on blackboards. Sometimes slow tectonic movements will force these chalky sediments above sea level. The White Cliffs of Dover are in England are perhaps the best known example of this. To find out more, read about Coccolithophores and White Cliffs of Dover and then play the video “Chalk Dust.”
http://serc.carleton.edu/eslabs/carbon/6a.html
“The ratio between the concentrations of nitrogen, phosphorus and silicate in particular areas of the ocean dictates competitive dominance within phytoplankton communities. Each ratio essentially tips the odds in favor of either diatoms or more other groups of phytoplankton, such as coccolithophores. A low silicate to nitrogen and phosphorus ratio allows coccolithophores to outcompete other phytoplankton species; however, when silicate to phosphorus to nitrogen ratios are high coccolithophores are outcompeted by diatoms. The increase in agricultural processes lead to eutrophication of waters and thus, coccolithophore blooms in these high nitrogen and phosphorus, low silicate environments.”
http://en.wikipedia.org/wiki/Coccolithophore
“Mission scientists believe 80 percent of eruptive activity on Earth takes place in the ocean, and most volcanoes are in the deep ocean. Until this discovery, NOAA and NSF had sponsored research on submarine volcanoes for 25 years without observing a deep-ocean eruption. Scientists believe further study of active deep-ocean eruptions will provide a better understanding of oceanic cycles of carbon dioxide and sulfur gases, how heat and matter are transferred from the interior of the Earth to its surface, and how life adapts to some of the harshest conditions on Earth.”
http://www.noaanews.noaa.gov/stories2009/20091217_volcano2.html
Michael Moon
You reject 3 million measurements at your peril, as they may have been not sufficiently random nor well enough distributed? Well were they or were they not?
Glass electrode pH measurements are of no value at all to measure a theoretical trend (based on established ocean chemistry) of 0.05 pH unit over the period 1850-1984. That is clear.
Some of the historical measurements done still may be of value if the more precise calculated pH values are used and can be compared for repeated cruises over the same stretch and seasons. But that is a lot of research work.
You are up on your high horse, American expression, but why?
I had a similar discussion with the late Ernst Beck about his compilation of the 900,000 historical wet chemical CO2 measurements: bad accuracy, wrong place of sampling, etc.
His compilation did show a CO2 “peak” of 80 ppmv around 1942, the equivalent of burning down 1/3rd of all land vegetation and regrowth in a few years time. That doesn’t show up in any high resolution ice core or any other proxy (including stomata data, beloved by some here…). The “peak” was simply because of questionable accuracy and mainly because of high variability at contaminated places for sampling.
See: http://www.ferdinand-engelbeen.be/klimaat/beck_data.html
If one is accusing Sabine and Feely of fraud, based on bad data, then skeptics are shooting in their own foot, only strengthening the believe of warmistas that all skeptics are conspiracy theorists…
Engelbeen your analogies are worthless.
Michael, the glass electrode measurements show variations of 0.2 pH unit from one year to the next (even excluding the extremes). To reach such a drop of pH in all oceans at the same time, you need a change of 200 ppmv CO2 extra in the atmosphere within a year for lowering pH and -200 ppmv for one-year changes in the opposite direction. Or changes of +/- 16°C to have the same effect from temperature changes. Other possible sources like (undersea) volcanoes are one-direction and may cause a fast drop in pH, but no rapid rise in pH, as the glass electrode data show…
Thus the glass electrode pH measurements simply are too unreliable to draw any conclusion of them…
Engelbeen, ocean chemistry is complex. The oceans are not well-mixed. There is significant variation in pH from place to place, season to season. Nevertheless decades of pH measurements have been recorded. You suggest they are Useless? I suggest that your contention is absurd. Newer more accurate instruments having been developed, do we now throw out decades of recorded data? Not where I come from, we don’t…
Michael,
There are lots of data from the past which still are valuable like pCO2, DIC, TA,… If they have measured total alkalinity and total carbon, it is possible to calculate the pH of that moment at the place of sampling. If one can combine that with repeated measurements at the same place around the same period of the year, then one can calculate the difference over the years. But I am afraid that this is a lot of work nobody likes to do…
As said, I have had a similar discussion about historical CO2 measurements: Most of the 900,000 historical measurements are only good to be discarded: in the middle of Paris, forests, below growing crops, etc. There were a few thousand done over the oceans and coastal with wind from the sea: these are usable and all show values around the ice core average CO2 levels…
When you bin data and exclude it from the analysis you should document your quality test so that others can validate that the data quality test was done correctly and is repeatable. The method and reasoning for data binning can also then be debated and challenged. If the binned data when included changes the result then you better have a water tight case for excluding it.
[OT . . mod]
Well speaking of using calculated values rather than measured data, the graph of arctic temperatures at http://ocean.dmi.dk/arctic/meant80n.uk.php seems to be based on models and calculations rather than actual data. At least that’s what I understand from reading the notes that accompany the data. If I’m mistaken I hope someone will correct me.
From DMI: http://ocean.dmi.dk/arctic/documentation/arctic_mean_temp_data_explanation_newest.pdf: “An NWP analysis is based on vastly more information than available from any single observing system. Data from ground, aircraft, bouys, ship, satellites, radiosondes, etc. are all combined to adjust the first guess field. As a consequence the quality of an analysis is much better than what can be obtained from gridding, or treating in other ways, data from a single or a few observing systems.
It seems that if there is any “pHraud” here it is in the WUWT articles (this one and the original at http://wattsupwiththat.com/2014/12/23/touchy-feely-science-one-chart-suggests-theres-a-phraud-in-omitting-ocean-acidification-data-in-congressional-testimony/).
I can find no replacing of modeled data with real data. The original graph at http://www.pmel.noaa.gov/co2/file/Hawaii+Carbon+Dioxide+Time-Series is labelled “Hawaii Carbon Dioxide Time-Series” with no claim about global applicability. It shows only actual high-quality times series data for Hawaii: the atmospheric CO2 data from Mauna Loa beginning in the 50’s and the ocean data for Station Aloha established in the 80’s. To that extent the figure is completely consistent with best scientific practice. The only deficiencies I see is that it is not clear if the lines through the data are curve fits or modeling results and that, so far as I can tell, “R.A. Feely, Bulletin of the American Meteorological Society, 2008” does not exist. But both of those are issues with NOAA’s presentation of the graph and may not be Feely’s fault.
While I am at it, at the Qwest link http://science.kqed.org/quest/2014/12/12/ocean-acidification-and-marine-life/ states that “The acidity of a solution is often reported in terms of pH. The pH scale ranges from 0 to 14. A value below 7 is acidic and a value above 7 is basic. The more acidic a solution, the higher the concentration of hydrogen ions and the lower the pH” and “It’s important to note that the pH of the ocean is still basic (around a pH of 8), but scientists use the term ocean acidification to indicate the increase in hydrogen ions in the ocean, which lowers the ocean’s pH”; all of which is perfectly correct and seems to be taking care to not mislead.
Generally, Anthony Watts does a commendable job. He seems to have blown this one.
Sorry about url’s rather than proper links. I could not figure out how to do the latter here.
Anything titled “ocean acidification” quite naturally will define it incorrectly. Acidification means making something acid.
Altering the pH down dies not make a basic solution acid unless it lowers it below 7.
Why is that so hard to understand?
It is so hard to understand because it is wrong. Lowering the pH of a solution is making it more acidic. It does not matter if the pH is greater than or less than 7. pH 8 is more acidic than pH 9, even though both are basic. It is the same as saying that -20 C is warmer than -30 C even though both are cold.
I have been a chemist for nearly 40 years and a chemistry professor for more than half that time. The above is standard usage in chemistry.
You are a confused fellow when you say pH 8 is more acidic than pH 9.
Properly, you should say pH8 is less basic.
As there is an extended chemical equilibrium going from CO2 to carbonic acid to bicarbonate to carbonate to calcium carbonate, if more CO2 is added, the equilibrium is pushed to the product side, more calcium carbonate. And, notably, any protons released in this process cannot alter this equilibrium.
An equilibrium CANNOT influence itself. But, that is exactly what the global warmists are trying to foist on the public. Only an outside source of protons could have the effects they claim.
Furthermore, organisms have physiological power such that they can handle and control the CO2 and/or carbonate they let into their cells and have intimate control of what they do with it. As calcium carbonate is less soluble in warm water than cold, warm waters are basically saturated with calcium carbonate, which is why coral reefs tend to concrete together.
The bottom line is that higher CO2 and warmer waters is heaven for corals. They thrive everywhere; the world’s corals are growing 30–50% faster now than they were 50 years ago.
Highley7, make a saturated solution of soda or baking soda and add some vinegar: a lot of CO2 is bubbling up.
If you add CO2 to the oceans, that pushes the equilibria to the carbonate side, but also releases H+ ions, which push the equilibria back to the CO2 side. The net effect is less carbonate and more bicarbonate and a slightly lower pH…
But if that will have much effect on sea life is questionable, as most calcifying organisms (corals, coccoliths) were thriving in much higher CO2 levels of the atmosphere.
higley7 wrote “if more CO2 is added, the equilibrium is pushed to the product side, more calcium carbonate”. That is wrong. One way to look at it is the way Ferdinand describes. A simpler way to look at it is to recognize that CO2 is an acid and carbonate is a base, so what happens is that they react with each other:
CO2 + CO3– + H2O = 2HCO3-
higly7 wrote “Only an outside source of protons could have the effects they claim”. That is true. The outside source of protons is CO2 added to the hydrosphere. CO2 is an acid (technically, a Lewis acid but not a Bronstead acid). It reacts with water to form carbonic acid:
CO2 + H2O = H2CO3
which dissociate to provide hydrogen ions
H2CO3 = H+ + HCO3-
higly7 wrote “Furthermore, organisms have physiological power such that they can handle and control the CO2 and/or carbonate they let into their cells and have intimate control of what they do with it”. That is true. They may have to work a bit harder to get the carbonate they need for their hard parts, but they will find it easier to get the carbon needed for photosynthesis. Near future levels of CO2 will likely not be any great problem, but if CO2 gets high enough (probably around triple CO2) to exhaust the buffering capacity of the ocean, things get worrisome.
Mike M,
“CO2 + CO3– + H2O = 2HCO3-“
or, to extend further, the reaction of real concern is
“CO2 + CaCO3 + H2O = Ca++ + 2HCO3-“
And H+ does not appear. That’s why I think fussing about accuracy of pH measurement is pointless. The direct measures of progress of the reaction are DIC and TA. These are just measured by quantitative chemistry on abundant species. If you really do want to use pH as a measure, it is better to infer it from the things you really want to know about than mess with more direct but unreliable methods.
Nick Stokes wrote: “The direct measures of progress of the reaction are DIC and TA. These are just measured by quantitative chemistry on abundant species. If you really do want to use pH as a measure, it is better to infer it from the things you really want to know about than mess with more direct but unreliable methods.”
That may well be true, It seems to me that you want to measure Dissolved Inorganic Carbon, Total Alkalinity, pH, temperature, and salinity and make sure that everything is internally consistent. I tool a quick look at the Station Aloha web site and it seems that all those things are measured, but I did not look at how the data are processed.
http://hahana.soest.hawaii.edu/hot/methods/results.html
Bermuda only used calculated pH based on TA and DIC, Hawaii did both, overlapping direct measurements (until 1992 electrode, not reported anymore, after that colorimetric) with calculated pH:
http://www.pnas.org/content/106/30/12235.full.pdf
Explanation of the methods at Bermuda (calculated pH in chapter 2.7):
http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
The post has generated a lot of discussion and I was impressed by , and to be honest a little sceptical of, the accuracy claimed by Ferdinand Engelbeen for colorimetric methods of pH assay . Certainly the glass electrode has been responsible for many attacks of frustrated anger by practising chemists and is not well loved , but I did not think that a test based on the customary indicator dyes (such as those used in test strips) could ever give better than +/- 0.2pH. Not , that is, until I came across the following open access paper for a dye based home built LED photometer with a claimed accuracy of 0.01pH units in the seawater range
http://www.sciencedirect.com/science/article/pii/S0304420314000061
Just how practical it is in the field or whether it is capable of automation for a sensor array in practical marine situations I do not know , but it is an improvement on the glass electrode IMO and deserves our support.
He Mike, most more accurate pH data since 1984 (and before) were obtained by calculation derived from Total Alkalinity and total carbon (DIC) which are far easier to obtain. Bates claims better than 0.2 % for both for the Bermuda series, giving a result for the pH reproducibility of better than 0.02 pH unit.
Therefore, claiming “fraud” for not using pH data accurate (with a lot of effort) to not better than 0.1 pH unit looks a little premature…
But indeed, there are already steps ahead of that:
The latest colorimetric techniques are reaching 0.001 pH unit accuracy…
http://www.sciencedirect.com/science/article/pii/S0003267013006570
NOAA agree that the oceans are being acidified, which is hogwash. Well it is NOAA. LOL
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Calling this phenomenon “ocean acidification” when surface seawater will remain “basic” under future emissions scenarios is alarmist
Just as we describe an increase in temperature from -40°F to -20°F as warming, even though neither the starting nor the ending temperature is “warm,” the term “acidification” describes a direction of change (i.e. increase) in the level of acidity in the global oceans, not an absolute end point. When CO2 is added to seawater, it reacts with water to form carbonic acid (H2CO3); hence acid is being added to seawater, thereby acidifying it. Similarly, in the example about human blood, a drop in pH is referred to as acidosis, even though the point where acidemia begins (7.35) is still above 7.
As I said upthread, acidification does not have a misleading denotation (formal definition), but it has a misleading connotation (associated implications). What to do? Put “acidification” inside quotation marks.
ocean acidification is used not because scientific value but becasue in this most politicized area of ‘science’ it has a significant impact and so a real marketing value . Not usual has climate ‘science’ amongst its others horrible approaches, has long practised science by press release and to be fair to climate ‘scientists’ many have got rather good at knowing what line to feed the press to get the rights results , no matter how actually poor the a papers contents .
NOAA … a US government agency … involved in temperature data manipulation and fraud … so why would it not be the same when it comes to the pH of oceans????
Same reason given by the Australian Bureau of Meteorology when they were caught red handed changing historical data with an algorithm that converted the trend from cooling to warming. Temp data from cold places is also deleted (giving a warmer average) by certain officials to give hottest year ever warcries and the excuse given is that the data was unreliable.
Here, “insufficient quality” means “incapable of supporting an obviously true hypothesis,” the proof being that it contradicts the hypothesis, thus demonstrating its unsuitability, sort of like what those guys did in excluding all but one tree in a dataset so that an obviously true hypothesis would not be falsified.