pH Sampling Density

Guest Post by Willis Eschenbach

A recent post by Anthony Watts highlighted a curious fact. This is that records of some two and a half million oceanic pH samples existed, but weren’t used in testimony before Congress about ocean pH. The post was accompanied by a graph which purported to show a historical variation in ocean pH.

I was unimpressed by the graph in that post, which seemed simplistic and, well, in a word, wrong. But on the other hand, I certainly found it bizarre and most interesting that someone would throw out that huge amount of scientific data. That was the reason I forwarded it to Anthony, in the hope of unraveling the actual truth of the matter.

So … as is my wont, I’ve now taken a look at the data myself, albeit at the moment a very preliminary look. The data was conveniently provided by a WUWT commenter in .csv format here, my compliments to him for the collation. He also has a good explanation of the process, along with R code. Note that there has been no quality control on the data. About 2% of the surface pH values are well outside the range of oceanic pH, and I removed them before looking further at the data.

Now, the first question I asked was, where were the samples taken? The problem with the graph in the recent post linked to above is that it lumps together samples taken in various parts of the planet. And unless the sampling is uniform in time and space, this is a Very Bad Idea™.

So I made a map that shows where each surface sample was taken. For simplicity, and because this was my first cut, I restricted myself to those samples with a depth of 0 (right at the surface), which are a bit less than a tenth of the total samples. Here are two different views of the same location data.

Sampling Density Map Surface pH Atlantic Sampling Density Map Surface pH

Figures 1a and 1b. Two views of the location of the surface samples of the global pH dataset, centered on the Pacific and the Atlantic. In some regions you can see the tracks of the oceanographic expedition  vessels quite clearly.

Now, I must confess that this was a surprise to me. I hadn’t expected the concentration of samples around Japan, it appears the Japanese oceanographers mush have been quite busy. And I also hadn’t expected the high sample density in the Baltic Sea and the other enclosed seas (the Black Sea between Turkey and Russia, and the Caspian Sea to its right).

Finally, here are the average pH values by gridcell, for the entire period of record

average ph by gridcellFigure 2. Average values of pH by gridcell in the record.

Now, you can see from these maps that we cannot simply put all of that data into a single box and extract a timeline from it.

So … was there “pHraud” in not utilizing this data? I say no, there was no fraud. I say this in part because it’s so difficult to infer intent. Because I have been falsely accused of having bad intent a number of times, I’m sensitive on the subject. I dislike accusations without evidence, and I see no evidence of fraud in this case.

However, it is a huge scientific resource, two million plus pH samples taken by oceanographers over decades, and not using it without some solid scientific reason for ignoring it just doesn’t work for me. What I suspect has happened is that the mass and complexity of the data was too overwhelming, and so the investigators simply put it into the “Too Hard” pile. But that’s just speculation, the real reason may be entirely different. Regardless of the reason, I do think that the authors should have explained their omission.

In any case, that’s the story so far. It certainly appears to me that there is plenty of data there for meaningful time series extractions in some areas. There are, for example, about 400 1°x1° gridcells that have more than a hundred observations per gridcell, and groups of nearby gridcell cells combined have much more data. The North Atlantic and the oceanic area off of Japan seem like they would have more than adequate data for time series extraction.

I may or may not do any followup on this dataset, but I invite readers to use the data for their own analyses.

Regards to all,

w.

ADDENDUM: As usual, I request that if you disagree with someone, please have the courtesy to QUOTE THEIR EXACT WORDS THAT YOU DISAGREE WITH, so that we can all understand the exact nature of your objections.

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rgbatduke
December 30, 2014 2:30 pm

What about dates? The assertion is that the pH is decreasing, right? So there has to be a trend. Second, a flat average is meaningless. The data has to be kriged, and from the look of the graph, there are (as usual) huge regions that are undersampled and smaller ones that are heavily oversampled.
rgb

Nick Stokes
Reply to  rgbatduke
December 30, 2014 4:13 pm

Yes, dates are essential. The authors didn’t say the earlier data didn’t exist. They declined to cite an annual average. That would mean they believe there wasn’t enough good data in that year, with adequate spatial coverage, to compute an average. That is what has to be checked.
GISS gives a global temperature average starting 1880. There is plenty of data from some places before 1880, but they don’t think the coverage is good enough for a global average. No one seems to think that is improper.
“Note that there has been no quality control on the data. About 2% of the surface pH values are well outside the range of oceanic pH, and I removed them before looking further at the data.”
Sounds like an important caution. Sabine et al may know stuff about data quality that experts here don’t.

Lance Wallace
Reply to  Nick Stokes
December 31, 2014 6:45 pm

Nick–
This graph seems to show that for the period from 1960-1980 when there were a large number of measurements there was small annual variation in pH, but both earlier and later when the number of measurements dropped off there was more variation.
https://dl.dropboxusercontent.com/u/75831381/pH%20vs%20time%20and%20number%20of%20obs.pdf

E.M.Smith
Editor
Reply to  Nick Stokes
January 2, 2015 8:05 am

Nick, “No one seems to think that is improper.”
I think that is improper. I’m not “no one”.
https://chiefio.wordpress.com/2011/07/01/intrinsic-extrinsic-intensive-extensive/
ANY “Global Average Temperature” is an absurd and non-physical number. Every single one.
So all you can do is FIRST and FOR ANY ONE THERMOMETER compute an anomaly trend; then average those trends and talk only about anomaly trends. (I hear 1000 keyboards preparing to say that is what is done… it isn’t.) Now realize, that means you must NOT average the Min-Max per day, and NOT average the days per month. Then NOT carry those monthly averages AS “temperatures” through the rest of your homogenizing (as GIStemp does) and only calculate a “grid cell anomaly” at the end (as GIStemp does).
Given all that machination, and all that fundamentally dumb (i.e. irrational) averaging of an intrinsic property (that can not be averaged and retain meaning as a temperature) it is highly irrational to ‘cut off’ the series at any point, or to use it with any variation in instruments in place (and expect more “averaging” to fix the induced discontinuities). It is fundamentally improper to use ANY variable set of thermometers and average them.
For a bit more depth:
http://www.uoguelph.ca/~rmckitri/research/globaltemp/globaltemp.html
http://www.uoguelph.ca/~rmckitri/research/globaltemp/GlobTemp.JNET.pdf

ABSTRACT:
Physical, mathematical and observational grounds are employed to show that there is no physically meaningful global temperature for the Earth in the context of the issue of global warming. While it is always possible to construct statistics for any given set of local temperature data, an infinite range of such statistics is mathematically permissible if physical principles provide no explicit basis for choosing among them. Distinct and equally valid statistical rules can and do show opposite trends when applied to the results of computations from physical models and real data in the atmosphere. A given temperature field can be interpreted as both “warming” and “cooling” simultaneously, making the concept of warming in the context of the issue of global warming physically ill-posed.

Ross is not “no one” either…
Per pH variation
It is also essential that Time Of Day and level of sunshine is known. Daily pH cycling in surface ocean levels can be fairly large based on relative photosynthesis / respiration of the stuff living in it… So if you do not know the TOD profile and the insolation levels, you might be only indirectly measuring sunshine and fertilizer…

Nick Stokes
Reply to  Willis Eschenbach
December 30, 2014 5:52 pm

Well, I’ve downloaded the data. I allowed down to 1 m depth (not just 0) and got 202354 points (min pH 0). I did a table over years. No QC.
I don’t think this was Sabine’s data. There is very little after about 1990; it’s mostly between then and 1960. Best year was 1978 with 7106 total.
Now even if that was uniformly distributed, it would be far too little. People here complain about the reduced size of GHCN. That has about 1800 stations with about 12 readings per year. And they are reasonably well distributed. Here we have at least double the area, and at best about 1/3 the points, with obviously eccentric distribution. And then with QC…

Here's the count, straight from R - format will probably be terrible:
1910 1912 1913 1914 1921 1922 1923 1924 1925 1926 1927 1928 1929 1930 1931 1932
  26    6   18   65   73  142  112   40  315  287  417  591  547  810  746 1310
1933 1934 1935 1936 1937 1938 1939 1940 1941 1942 1943 1944 1945 1946 1947 1948
1184 1232 1433  997  772  715  553  680  867   31  159   68   79  254  178  383
1949 1950 1951 1952 1953 1954 1955 1956 1957 1958 1959 1960 1961 1962 1963 1964
 549  972  532  312  353  751 1090 1087 1261 2379 2990 2373 1668 1808 2650 3387
1965 1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 1976 1977 1978 1979 1980
4965 3603 4621 4778 5027 5057 6959 6756 6175 6190 5423 6481 6583 7106 5633 6807
1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996
6594 7049 6908 6064 4550 4504 5538 5836 3902 4411 2677 1477 1692 1546 1485 1278
1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011 2012
 876  846  707  637  454  269  237  136  207  274  145  232  103  121    5  108
2013
  70

[Reset to ASCI “pre” format. .mod]

Nick Stokes
Reply to  Willis Eschenbach
December 30, 2014 6:31 pm

Thanks, mod – I’ll try to remember that.

Lance Wallace
Reply to  Willis Eschenbach
December 30, 2014 6:37 pm

Nick Stokes’ table of pH measurements by year shows a sharp drop in the number of surface measurements from about 5800 in 1988 to 1500 just 4 years later and down further to the ridiculously small number of about 150 by the year 2007. Strangely enough, this is the exact period (1989-2007) chosen by Feely to illustrate the drop in pH:
http://wattsupwiththat.com/2014/12/23/touchy-feely-science-one-chart-suggests-theres-a-phraud-in-omitting-ocean-acidification-data-in-congressional-testimony/
The graph of pH vs year by Mike Wallace also shows a sharp drop, more like a step function, in pH values between about 1989 and 2004, again coinciding with the major reduction in the number of measurements:
https://docs.google.com/document/d/1ijyZwW2e_OJEwJiimgnO-UF9WF_1k_2GWfnhYThq2O0/edit#heading=h.1jqf6pash65r
If one wanted to make the case for ocean acidification, there is really only one place to do it, and that’s from 1989 on.

Nick Stokes
Reply to  Willis Eschenbach
December 30, 2014 6:43 pm

Lance W,
“Strangely enough, this is the exact period (1989-2007) chosen by Feely to illustrate the drop in pH:”
Yes, but the dataset is the one chosen by Mike Wallace, with all the “omitted data”. It’s unlikely to be what Feely was using for the post-1988 period.

AlexS
Reply to  Willis Eschenbach
December 30, 2014 11:53 pm

” People here complain about the reduced size of GHCN. That has about 1800 stations with about 12 readings per year. And they are reasonably well distributed. ”
Ahaha! Really, how many of them are in the middle of oceans?

richardscourtney
Reply to  Willis Eschenbach
December 31, 2014 1:40 am

Nick Stokes:
I write because it is rare for me to agree with you so I welcome this opportunity to do it.
You say

Well, I’ve downloaded the data. I allowed down to 1 m depth (not just 0) and got 202354 points (min pH 0). I did a table over years. No QC.
I don’t think this was Sabine’s data. There is very little after about 1990; it’s mostly between then and 1960. Best year was 1978 with 7106 total.
Now even if that was uniformly distributed, it would be far too little.

Emphasis added by me: RSC
I very strongly agree and I have repeatedly made the same point about this data – including making it on WUWT – whenever Ferdinand Engelbeen has cited this data.
The data is far too sparse in spatial distribution and over time for it to be meaningful as indicator of the putative alteration of average oceanic pH resulting from increase to atmospheric CO2 concentration over the last century.
Richard

Reply to  Willis Eschenbach
December 31, 2014 2:24 am

Lance, the graph of the other Wallace is solely based on glass electrode pH measurements, which are near completely abandoned in recent years as too unreliable (with a lot of care not better than 0.1 pH unit) to measure a general pH drop of theoretically 0.1unit since 1850 (with about 50% of the CO2 increase since 1984 in the atmosphere) since the start of the industrial revolution. Moreover his pH drop of 0.3 pH unit since 1984 is not the result of a global or local pH drop, it is the result of the random sampling in different places and different seasons.
The curves by Sabine, Feely, Bates and many others are based on either calculated pH, or pH measurements based on far more accurate colorimetric pH measurements or both. They excluded glass electrode pH measurements as too unreliable.
pH can be calculated by (over 80 years) established ocean carbon chemistry from other, better defined measurements like TA (total alkalinity) and DIC (dissolved inorganic carbon).
See: http://www.pnas.org/content/106/30/12235.full.pdf
for a description of the methods and the trends at Hawaii, where both methods were used.
Before 1992 direct pH measurements were by glass electrode:
http://hahana.soest.hawaii.edu/hot/methods/ph.html
but not used in their graphs
For Bermuda:
http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
computation of pH is mentioned in chapter 2.7
More data for several fixed stations can be found at:
http://www.tos.org/oceanography/archive/27-1_bates.pdf
Then the data for regular sea cruises by research ships, here for Japan:
http://www.data.jma.go.jp/kaiyou/english/oa/oceanacidification_en.html
And there is an interesting PH.D. work about the results from cruises in the Southern Oceans which tries to combine pH measurements with calculated pH over time (-0.03 +/- 0.03 pH unit since 1972):
http://scholar.colorado.edu/cgi/viewcontent.cgi?article=1456&context=honr_theses
which contains many interesting points and graphs. Especially the graphs of the distribution in time and latitude of the measured and calculated values (page 46) is interesting.
More to learn about carbonate chemistry in the oceans in a nice overview:
http://www.soest.hawaii.edu/oceanography/courses/OCN623/Spring2012/CO2pH.pdf

Reply to  Willis Eschenbach
December 31, 2014 5:32 am

Richard,
The compilation by Wallace is unreliable, because he didn’t sort on place and seasons. Regular cruises over the same tracks give a better insight, even if done with less accurate equipment. It is better to recalculate pH from other, more frequently measured variables like TA and DIC, but that is a hell of a job to sort out.
Anyway, you don’t need to monitor all parts of all oceans frequently each year, as ocean chemistry is the same everywhere and the changes caused by (seasonal) temperature (and accompanied bio-life) changes level off after a full seasonal cycle. Ocean pH is directly influenced by atmospheric CO2 levels, which influence at any place of the oceans can be calculated if a few local variables are known. It would be quite strange if none-monitored open ocean places would show an increase of pH with increased CO2 in the atmosphere (far more variable at upwelling places and estuaries).
All fixed stations and repeated cruises show a declining trend since 1984. All in ratio to increasing CO2 levels in the atmosphere.
A compilation of Southern Ocean cruises (31,700 measured + 41,800 calculated pH values) also shows a declining trend since 1972.
(links are currently under moderation, will be shown soon).

James McCown
Reply to  Willis Eschenbach
December 31, 2014 7:04 am

Ferdinand Englebeen said:

Anyway, you don’t need to monitor all parts of all oceans frequently each year, as ocean chemistry is the same everywhere and the changes caused by (seasonal) temperature (and accompanied bio-life) changes level off after a full seasonal cycle.

I find this difficult to believe, Ferdinand. I know the salinity of the ocean varies quite a bit from location to location. And although salinity does not directly affect pH, I can believe the chemistry of the ocean that does affect pH also varies quite a bit by location.

JayKay
Reply to  Willis Eschenbach
December 31, 2014 8:50 am

What appears to be fraudulent about the Feely/Sabine study is that they apparently failed to mention that they had used mostly modeled data and that only the data since 1988 were measured. Had they been a bit more forthcoming in their study, they would have mentioned the existence of the full set of measurements and provided their rationale for excluding it. They also would have explained how they got the data they did provide in their time series plot. With the history of the IPCC climate models, there is good reason to have serious doubts about any modeled data.

Lance Wallace
Reply to  Willis Eschenbach
December 31, 2014 10:38 am

Ferdinand, thank you for the valuable references. I note that the NOAA website used by Simon Filiatraut to download 2.4 million pH measurements
(http://wattsupwiththat.com/2014/12/23/touchy-feely-science-one-chart-suggests-theres-a-phraud-in-omitting-ocean-acidification-data-in-congressional-testimony/#comment-1823345)
also offers various related measurements, including temperature, salinity, alkalinity, CO2 pressure, oxygen, etc. As you point out, these could be used to calculate an expected pH and therefore could serve as a quality control check on the pH values.
Although the carbon chemistry may give an indication of the effect on ocean pH of increasing CO2 in the atmosphere, much may also depend on the biological and geological feedback, so I am not convinced that we can estimate the future effect very well.

Reply to  Willis Eschenbach
December 31, 2014 2:20 pm

Lance, the data from NOAA were further gridded Berényi Péter in 5×5 deg boxes and found near zero trend over the past 30 years for all gridded boxes. The error margin still is large +/- 0.03 unit per decade for the glass electrode measurements, where the modern measured/calculated methods show a trend of around -0.015 unit per decade, largely within the error margins of the glass electrode measurements.
What we already can conclude is that the glass electrode pH measurements can’t show the trend over the past 30 years and that the compilation of the other Wallace doesn’t show a real pH trend, but the result of random sampling in place and time.
Indeed it should be possible to use the other historical measurements to calculate the pH of that moment. The last reference I sent was for a PhD work which has done that for all known data for the Southern Ocean. Seems a lot of work, but maybe programmable now that all data are in computer readable form…

Lance Wallace
Reply to  Willis Eschenbach
December 31, 2014 3:53 pm

Apart from the question of a trend, there are a few other aspects of the data set that seem of interest.
1. There is an odd rather symmetric relation of the measured pH to latitude, reaching a maximum of 8.1 at about 30 degrees N and S, dropping back to 8.0 at the equator, and also dropping below 8 toward the poles.comment image
2. The later years (1988 on) not only show a drop in pH, they also show a sharp increase in the median depth, fromd about 200 m to about 1000 m. And pH showed a significant Spearman correlation of -0.15 with depth, and a highly signficant though small Pearson regression coefficient of -0.01 per hundred meters. This might have played a small part in the Feely Sabine calculation dealing with these same years.comment image
3. Ferdy E., what direction do you expect the seasonal variation to take? In both hemispheres, it appeared that the lowest values were in summer and the highest in spring.comment imagecomment image

ferdberple
Reply to  Willis Eschenbach
January 1, 2015 5:43 pm

The data is far too sparse in spatial distribution
=============
sort of like using Mona Loa for global CO2?

Latitude
Reply to  Willis Eschenbach
January 1, 2015 6:33 pm

Ferdinand…their fig 4 pH from your Hawaii link….just looks like a sine wave…no steady decrease in pH at all
honestly, it looks like if they had started in 1979 and stopped in 2007, they would have shown a huge increase in pH
Looks like a temp graph where you cherry pick your time to show anything…and frankly, seeing it that way makes it clear that any wiggles in pH, either up or down, is just nothing more than that…..a wiggle
http://www.pnas.org/content/106/30/12235.full.pdf

Editor
Reply to  rgbatduke
December 31, 2014 7:25 am

Doesn’t krigging assume a smooth spread? Is there any reason to believe the ocean pH is properly represented by a smoothed even spread? a lack of “hot” or “cold” spots? spots of upwelling acidic or basic water from underwater features or events? should these be kirgged away? or krigged over?
Does the ocean even have “an average pH” that could be going up or down? or is this just another invented concept created for propaganda purposes — world in danger or world resilient? is it just another weapon in the Climate Wars?

richardscourtney
Reply to  Kip Hansen
January 1, 2015 1:24 am

Kip Hansen
You ask

Does the ocean even have “an average pH” that could be going up or down? or is this just another invented concept created for propaganda purposes — world in danger or world resilient? is it just another weapon in the Climate Wars?

I provide my answers to each of your three questions in turn.
Q1
Does the ocean even have “an average pH” that could be going up or down?
A1
Possibly, but probably not
(see comment by Lance Wallace at December 31, 2014 at 3:53 pm).
Q2
is this (i.e. “an average pH”) just another invented concept created for propaganda purposes — world in danger or world resilient?
A2
Yes.
Q3
is it (i.e. “an average pH”) just another weapon in the Climate Wars?
A3
Yes.
Richard

ferdberple
Reply to  rgbatduke
January 1, 2015 10:53 pm

The gridded result:
Berényi Péter December 31, 2014 at 8:58 am
A preliminary look at the data shows beyond doubt, that ocean pH is decreasing indeed, at a rate of -0.002±0.038/decade. In other words, it is absolutely stable.

delivers virtually the exact same answer as simply treating the data as a random sample, without any gridding, averaging, anomalies, adjustments, etc.
ferdberple December 31, 2014 at 8:29 am
http://oi60.tinypic.com/9s7xvo.jpg

December 30, 2014 2:33 pm

I’m sure I read a while back that if you record the PH in the morning and again in the evening, in the same place, the samples will show different data.

Streetcred
Reply to  Norm (@Old_Norm)
December 30, 2014 4:03 pm

That is true. There are many physical occurrences that impact pH … like surface agitation, for example.

Reply to  Streetcred
December 31, 2014 3:50 pm

Seawater pH changes with temperature, time of day, season, depth, light level, whether the sample is filtered or not… Diurnal variation in “A Shallow Texas Bay” as reported in RA Horne’s Marine Chemistry, 1969 was ~0.7.

oeman50
Reply to  Norm (@Old_Norm)
January 1, 2015 8:48 am

I agree, Norm. Actual pH will vary considerably due to temperature, salinity, calcium carbonate content, etc., which makes some previous comments about the chemistry of the ocean being the “same everywhere” suspect, IMHO.
One point I have not seen yet is the impact of the temperature compensation of electrode pH meters. Many meters have both electrode temperature and actual temperature compensations that are often set to correct the reading to 25C. I have no idea of what type of data we are getting. However, I know I would like to see the actual pHs, because that is what the sea life is encountering.
Last point about “average pH.” You might think the average of pHs 7.0 and 8.0 is 7.5. But due to the logarithmic nature of pH, the average is actually 7.26. So unless your averaging program first converts the pHs to actual H+ ion concentrations, then averages them and takes the log of the results, then you will not have accurate averaging.

December 30, 2014 2:34 pm

Can the data be resolved into decadal trends? In addition to “where”, “when” the sampling was conducted is crucial. The lower pH around the Bering Sea and northeastern Pacific could easily be dominated by upwelling events that are modulated by the PDO. Average pH could be skewed by the time of sampling.

December 30, 2014 2:36 pm

Thanks, Willis.
I agree that throwing out so much data needs explaining,
Maybe it just went overboard?
Happy new year!

spetzer86
December 30, 2014 2:38 pm

Could you please provide the cut off limits for the data considered outside normal sea pH?

December 30, 2014 2:38 pm

Willis
The methods for taking co2 samples since 1820 And up to the time that keeling started Sampling at mauna loa have been roundly criticised. Is the method for taking these ph samples considered robust and consistent bearing in mind the number, the time scale and the variety of people taking them?
Tonyb

tonyb
Editor
Reply to  Tonyb
December 31, 2014 1:08 am

good grief! The gremlins ate much of my comment above.
To paraphrase, bearing in mind the complaints about historic co2 readings that were regularly taken from 1820 up till Keeling changed the methodology in the 1950’s, can we be certain that these historic ph readings are robust?
tonyb

Reply to  tonyb
December 31, 2014 7:51 am

Hi Tony, ferdberple does show a plot of all sampled pH data over the years near the end of the discussion. Has a similar look as the cloud of CO2 data from the many samples taken in the past… pH data ranging from zero to 14???
I agree with Sabine: most of the data are not reliable but may give some idea if sorted for place and season…

Reply to  tonyb
December 31, 2014 8:16 am

Hi Ferdinand
Having just seen your post I have given my reply to fredberple here
http://wattsupwiththat.com/2014/12/30/ph-sampling-density/#comment-1825726
Tonyb

Latitude
December 30, 2014 2:43 pm

samples around Japan….whaling is scientific for them
8.25….higher than the buffer…..plankton??
There’s way too many 8.25’s….what’s up with that?

Latitude
Reply to  Latitude
December 30, 2014 2:44 pm

Willis, can you divide this from the time of formula measurements…and actual measurements?

michael hart
Reply to  Latitude
December 30, 2014 3:43 pm

8.25 is very close to the ideal buffering point, as illustrated here: http://water.me.vccs.edu/courses/env211/changes/carbonategraph.gif
That is of course why buffers are used to maintain pH close to a fixed point.

Latitude
Reply to  michael hart
December 30, 2014 4:47 pm

except that looking at the gridcell map Willis posted…..it’s not possible where it’s shown

tty
Reply to  Latitude
December 31, 2014 1:41 am

pH over 8.25 is not unusual in areas with high biologic activity where algae “eat” the CO2. Over coral reefs pH can touch 9.0 in late afternoon.

Bart
Reply to  Latitude
December 31, 2014 9:31 am

Mmm… I don’t think you will get very far asserting that Japan is a low-tech nation. I would advise eschewing that approach.

Latitude
Reply to  Bart
December 31, 2014 9:58 am

no one said that Bart???

Bart
Reply to  Bart
December 31, 2014 11:05 am

Then, I misunderstood. The meaning of the remark wasn’t clear to me. My apologies.

Latitude
Reply to  Bart
December 31, 2014 11:49 am

oh, I think I see what it was….
The Japanese use “scientific research” as an excuse for whaling, tuna, fisheries…
…so their commercial fishing fleet takes measurements every time they go out
That’s why the sample density is so high there..
Better??

Bart
Reply to  Bart
December 31, 2014 1:46 pm

Yes. Now it makes perfect sense. Good observation.

December 30, 2014 2:47 pm

Willis, there is something fishy in that ocean less-alkaninization.
The average ocean water contains 10,4 mmol/l ca2+ and 2.34 mmol HCO3-
http://www.seafriends.org.nz/oceano/seawater.htm
Obviously the solubility of caciumcarbonate at pH8 is 1mmol at 25C (fig 2):
http://www.ldeo.columbia.edu/~sanpisa/OceanSed%20project/factorscontrolcarbonate.htm
so it appears that the combined Ca2+ and HCO3 – are oversaturated but that is temperature/pressure and pH dependent. It occurs to me that adding additional CO2 would result in the precipitation of CaCO3 as it exceeds it’s solubility, rather than it would lower the pH.

Nick Stokes
Reply to  leftturnandre
December 30, 2014 4:04 pm

“It occurs to me that adding additional CO2 would result in the precipitation of CaCO3 as it exceeds it’s solubility, rather than it would lower the pH.”
You need to work with the solubility product here. Solubility .001M doesn’t help, because it assumes no excess ions present. The solubility product is that of Ca++ and CO3–. The reason added CO2 dissolves CaCO3 is that, which it adds carbon, it converts CO3– to HCO3-, thus reducing the product.

tadchem
Reply to  Nick Stokes
December 31, 2014 7:03 am

Carbon dioxide in solution forms a buffer solution with the form taken the carbon dioxide strongly dependent on pH:
CO2 + H2O H2CO3 (carbonic acid) upon becoming absorbed by water
At low pH it forms bicarbonate ion
H2CO3 H+ + HCO3- (balance point pH 6.37)
At intermediate pH bicarbonate forms carbonate
HCO3- H+ + CO3(-2) (balance point pH 10.36)
At higher pH it is predominantly present as carbonate.
At the prevailing pH of most sea water, about 8.3 to 8.4, the CO2 present in sea water is almost entirely present as bicarbonate, with barely 1% of it present as carbonic acid and another 1% present as carbonate ion.
This is good because the bicarbonate form is the only form biologically available for foraminifera, coral, mulloscs and other sea life that forms calcium carbonate structures.
CaCO3 ‘precipitated’ by sea water (eventually forming limestone, chalk, marble, etc.) was formed by living cells.

Latitude
Reply to  leftturnandre
December 30, 2014 5:35 pm

CA(HCO3)2 = CACO3 + CO2 + H2O

Oldseadog
December 30, 2014 2:51 pm

I think you are right, the enormous amount of data accumulated over a long period will take a lot of time to analyse and quite possibly will not come to the conclusion that the analysts would prefer.
On the other hand, there would be a PhD for someone with the integrity to do an honest breakdown and dissection of the data – assuming that they could find an academic establishment to review the result dispassionately.

jorgekafkazar
Reply to  Oldseadog
December 30, 2014 3:22 pm

I know of no academic establishment that is not a hotbed of activist bias. Individual researchers, perhaps, but not the average student.

Reply to  Oldseadog
December 31, 2014 7:58 am

There was a PhD work done on part of the data for the Southern Ocean (2012), partly on measured, partly on calculated data:
http://scholar.colorado.edu/cgi/viewcontent.cgi?article=1456&context=honr_theses
I suppose that he used all available data for the Southern Ocean, as that was very sparsely sampled in the past…
The result, with large margins of error: -0.3 +/- 0.3 pH unit over the period 1972-2011

Rob
Reply to  Ferdinand Engelbeen
January 9, 2015 11:47 am

This was a ‘senior thesis’ paper in receiving an undergraduate BS degree, and not a PhD. First couple of lines is all one needs to read to understand the direction of paper. Granted, most ‘senior thesis’ never come anywhere close to this attempt, but one also only needs to look at the principal ‘contributor’ as well (likely thesis adviser).

Garhy
December 30, 2014 2:51 pm

The Japanese have cultivated seaweeds for centuries and modern operations would be very interested in water conditions, including pH.
http://www.seaweed.ie/aquaculture/noricultivation.php
An interesting side note to the nori cultivation story is the honoring of Dr. Kathleen Drew-Baker whose research on the life cycle of nori (Porphyra umbilicalis) enabled better production and quality. The Japanese erected a statue of her and publicly remember her work over sixty years later. https://en.wikipedia.org/wiki/Kathleen_Mary_Drew-Baker

alf m meling
December 30, 2014 3:30 pm

“Now, you can see from these maps that we cannot simply put all of that data into a single box and extract a timeline from it.”
The same procedure used for the “global temperature” trend?

Bill Illis
December 30, 2014 3:36 pm

Go Willis go. This is (another) very important issue that needs an objective mind.

December 30, 2014 3:42 pm

Another issue is how long were sample maintained before pH was determined. Samples were often taken during cruises and then analyzed weeks to months later. There was no systematic timeline for nalaysis. Bottles locked away in the dark prevent photosynthesis that could increase pH, but cellular respiration from bacteria would continue and could create a drop in pH.

noaaprogrammer
December 30, 2014 3:44 pm

One should see wider seasonal and decadal variations with seas like the Black Sea that are more ‘landlocked’ than the open oceans. Most of the Black Sea’s bottom waters are devoid of oxygen. I would think that similar such situations be graphed separately, rather than dumping all data into one graph. Also, rates of inflow and outflow would have to be accounted for.

Robert of Ottawa
Reply to  noaaprogrammer
December 30, 2014 6:15 pm

In a local lake in the Gatineau Park, Canada, there is a lake which is a left-over from the last ice-age. It’s called Pink Lake, and the Oxygenated water only goes to 60 feet, below the oxy-xline, ithe water is oxygen free. Scuba diving i9s forbidden there.
http://www.ncc-ccn.gc.ca/places-to-visit/gatineau-park/pink-lake

Crispin in Waterloo
Reply to  Robert of Ottawa
December 31, 2014 8:23 am

New dams that have a lot of vegetation in the flooded area also have a poor distribution of oxygen. Below the oxy line there is a high concentration of H2S. If deep water is released from such a dam into the river below, it kills everything in it. Thus it is common to release some of the deep water and mostly top water while monitoring the mix downstream. It is easy to get it wrong.
Good dam management has to address this issue constantly. I suspect there must be a lot of lakes like Pink Lake in other parts of Canada. Being deep helps create such an unwanted boundary.

Andrew Hamilton
December 30, 2014 3:44 pm

What I suspect has happened is that the mass and complexity of the data was too overwhelming, and so the investigators simply put it into the “Too Hard” pile.
I aplolgise for not accepting this idea. You have managed to make something of it in a short timescale and I have no doubt that you or someone like you would be able to do much more if time was available. Time was available to the original ocean acidificationists and they chose not to do it. That tells me a lot.

Streetcred
Reply to  Andrew Hamilton
December 30, 2014 4:05 pm

+1 Andrew … if you have the real data then modelling fake data does not cut the mustard. Time is not of the essence.

mpainter
Reply to  Willis Eschenbach
December 30, 2014 4:57 pm

Willis says ” We don’t know at this point why the data weren’t used”
I thought we did. Sabine and Englebeen have said words to the effect that the data did not provide the “signal” that was sought, the signal being the decrease in oceanic pH. They wanted that “signal” and they had to fabricate the data to provide it. This was done by hind casting a trend of declining pH via modeling.

Reply to  Willis Eschenbach
December 31, 2014 4:52 am

You would think that any reasonably competent researcher setting out to look at global oceanic pH would be prepared to deal with large data sets over large areas. If not, how could they expect to produce valid results?

Reply to  Willis Eschenbach
December 31, 2014 6:07 am

mpainter, thanks for the alleged motives…
There are two problems with the data:
– the accuracy of the glass electrode pH measurements: 0.1 pH unit, while the theoretical trend from 1850 to 1984 was about 0.05 pH unit.
– the lack of data for the same parts of the oceans in the same seasons over a longer period.
The theoretical trend is confirmed since 1984 at seven fixed station at different places over the oceans, based on more accurate direct (colorimetric) pH measurements and calculated pH (which overlap each other).
The theoretical trend is confirmed since 1972 for the Southern Ocean based on direct (glass electrode) and calculated measurements (31,700 measured + 41,800 calculated pH values), be it with large margins of error: -0.03 +/- 0.03 pH units:
http://scholar.colorado.edu/cgi/viewcontent.cgi?article=1456&context=honr_theses
Here the distribution over time of the measurements:
http://www.ferdinand-engelbeen.be/klimaat/klim_img/ph_sh.jpg
no direct measurements in the period before 1990…
If you see any reason that the pH of the open oceans in general wouldn’t show a faint drop with increasing CO2 in the atmosphere in the period before 1984, I am very interested to hear it…

mpainter
Reply to  Willis Eschenbach
December 31, 2014 12:06 pm

Ferdinand :
The whole problem with climate science is that theory is substituted for facts and facts are invented. If you cannot see the fault of Sabine and Feely’s methods, then perhaps you share those faults. Do approve of the method of presenting model product as observed measurements, giving no hints of how the data was actually derived?

Reply to  Willis Eschenbach
December 31, 2014 2:33 pm

mpainter, I don’t see much problems by presenting modeled data for the period before 1984, because in this case the modeled data are much better than the measured data, which are widely around the model (contrary to climate models), where the (chemical) model is confirmed in the period after 1984.
The only point is that Feely/Sabine should have made it clear that the early part and the “future” part of the graph was from a model, because the observations were not accurate enough.

Admin
December 30, 2014 3:46 pm

Hi Willis, I appreciate you are trying to see both sides of the issue, but I find it difficult to imagine a legitimate reason for discarding, not even mentioning the data, and replacing it with a computational model which is based on – what?
I mean, try to imagine this in the context of a high school chemistry class. “Sorry teach, the practical experiment I did produced some difficult to analyse values, so I threw out the data and based my conclusion on a mathematical model of what I think should have happened … yes, I know I didn’t mention the data I discarded, but you see the data was no good… ” – that conversation would have rapidly concluded in an “F” for that assignment.
It might be that different rules apply when you producing reports which influence the expenditure of billions of dollars of taxpayer money, but I can’t help viewing such “lapses” from the perspective of what it would have meant to me, back when I was being taught about science.

Andrew Hamilton
December 30, 2014 3:50 pm

Has anyone attempted to calculate just how much carbon dioxide would be required to change the pH of the oceans to any significant extent? It seems to me that given the density of sea water and the volume of that water, compared against the equivalent values for atmospheric CO2 and the fact that CO2 in aqueous solution is a weak acid, never mind the ample buffering in the oceans, the numbers calculated for carbon dioxide requirements would be very large indeed.

Rick Rezabek
Reply to  Andrew Hamilton
December 30, 2014 4:18 pm

Indeed. I did a simple calculation during the BP oil spill in the Gulf of Mexico. It was a tragedy, no question, but the amount of oil spilled there was on the order of one drop per billion (sorry, don’t have the numbers anymore). The oceans are massive, it takes massive amounts to ‘Fundamentaly” change them.

Reply to  Andrew Hamilton
December 30, 2014 4:37 pm

… and why assume that CO2 is the only mechanism that could possibly move oceanic pH towards neutral?

Alx
Reply to  nielszoo
December 30, 2014 4:50 pm

Because.
That’s it. Because.
It’s the CO2.
Because.

Reply to  nielszoo
December 31, 2014 6:19 am

Because the increase of total carbon (DIC, CO2 + bi + carbonate) in the ocean surface is measured…
If the pH drop was caused by e.g. undersea or land volcanoes (SO2, HCl, HF,…) the pH would drop and expel CO2 (reducing DIC). If the pH drop is caused by more CO2 in the atmosphere, DIC increases…

Reply to  Andrew Hamilton
December 31, 2014 6:30 am

That calculation is made and quite easy to do: one can even calculate the pH from the oceans during an ice age (8.367). All you need is the amount of CO2 in the atmosphere: that is in fast equilibrium with the CO2/bi/carbonate system in the ocean surface and the rest is established ocean carbon chemistry of already 80 years ago:
http://biocycle.atmos.colostate.edu/shiny/carbonate/

Reply to  Ferdinand Engelbeen
December 31, 2014 6:34 am

Sorry, forgot to add: the increase of 110 ppmv (30%) in the atmosphere gives an increase of DIC of about 3% in total carbon (DIC) in the “mixed” layer of the oceans (0-200 m depth), depending of the Revelle/buffer factor. That gives a change of about -0.1 pH unit since 1850. The exchange with the ocean surface layer is very fast (1-3 years), with the deep oceans much slower.

richardscourtney
Reply to  Ferdinand Engelbeen
January 1, 2015 1:40 am

Ferdinand Engelbeen
You say

That calculation is made and quite easy to do: one can even calculate the pH from the oceans during an ice age (8.367). All you need is the amount of CO2 in the atmosphere: that is in fast equilibrium with the CO2/bi/carbonate system in the ocean surface and the rest is established ocean carbon chemistry of already 80 years ago:
http://biocycle.atmos.colostate.edu/shiny/carbonate/

Well, yes, the calculation is “quite easy to do” and it does give an answer, but the answer is probably wrong (both for the present situation and for “during an ice age”).
“That calculation” assumes that only inorganic chemistry is affecting ocean pH but – in reality – it is observed that biota affect ocean pH, too.
Richard

richardscourtney
Reply to  Ferdinand Engelbeen
January 1, 2015 1:49 am

Ferdinand
I see Willis has also refuted your assertion here and supported it with a real-world illustration here.
Richard

Reply to  Ferdinand Engelbeen
January 1, 2015 2:58 pm

Richard, the data of Willis show a higher increase of DIC than I reported as the real ratio depends of the “Revelle” (buffer) factor and temperature which changes with latitude. Anyway, the 30% change of CO2 in the atmosphere gives the same change as free CO2, but a much smaller change in total CO2 (DIC) and a very small change in pH.
That can be seen for the different stations:
http://www.tos.org/oceanography/archive/27-1_bates.pdf
Fig. 3 and Table 2.

jim2
December 30, 2014 3:55 pm

I suppose you could use the methods of BEST on this. The methods are published.

Tony
December 30, 2014 4:09 pm

I assume the data have been averaged to produce the earlier graph? Given that pH is a negative log of a concentration, how is the averaging carried out?
How meaningful is any such average, especially in a buffered solution such as sea water?

Gail Combs
December 30, 2014 4:20 pm

The analysis was done here:
http://www.co2web.info/ESEF3VO2.htm
Acidification is not really possible in a buffered solution like the ocean. Yes you will get local highs and lows but they will not last. The only way you can get a buffered solution to change pH permanently is to use up all the buffering agent. I know since I used to analyze Deionized river water where the organic content buffering the water changed on a daily basis.
Also consider basalt as a buffering agent as well as limestone.
Seems since all the rest of the ‘evidence’ has proven to be junk they are trying to recycle the tired old ‘Ocean Acidification’ again. I though that beast had already been slayed.

Latitude
Reply to  Gail Combs
December 30, 2014 4:36 pm

+1…thank you Gail for nailing another one
“The only way you can get a buffered solution to change pH permanently is to use up all the buffering agent”
…and you can only do that in the lab

Reply to  Gail Combs
December 30, 2014 6:39 pm

Gail, this is not a conventional buffer system which you’d find in the lab. In a normal buffered solution the pH is close to the pKa value for the buffer, being a diprotic acid carbonic acid has two pKa’s, 6.3 and 10.3, the ocean is nowhere near these! Addition of CO2 changes the equilibrium system of the ocean towards lower pH.

Latitude
Reply to  Phil.
December 31, 2014 4:46 am

…assuming the buffer is no being constantly replaced
which it is

Nick Stokes
Reply to  Gail Combs
December 30, 2014 7:21 pm

“The only way you can get a buffered solution to change pH permanently is to use up all the buffering agent.”
That isn’t true at all. Every time you add acid or base, you shift the pH. The rate of change is reduced by the buffer, but not to zero. The formula is Henderson–Hasselbalch:
pH=log(pKa)+log([A-]/[HA])
for acid HA.
The graph of this is called a Bjerrum plot. You can calculate the seawater pH changes here.

Jaakko Kateenkorva
Reply to  Nick Stokes
December 31, 2014 12:25 am

The rate of change is reduced by the buffer, but not to zero.

As if drawing a parallel between cAGW and homeopathy wasn’t irresistible enough. There is one significant difference though: homeopathy aims to heal people.

Leonard Weinstein
Reply to  Nick Stokes
January 1, 2015 6:37 am

Nick, that again assumes all buffering is chemical. Biological activity is not included, and likely changes the result. In addition, if surface winds change over time, the mixing depth changes, and affects the surface average.

Mike M.
Reply to  Gail Combs
December 30, 2014 7:29 pm

Adding acid to a buffer will lower the pH and adding base will raise the pH, but the changes will be less than without buffer. That is basic introductory chemistry. With a well designed buffer (equal amounts of acid and conjugate base and a reasonably high concentration of both) the pH changes can be very small. But the ocean is not such a buffer. The bicarbonate concentration is a little under 2 mmol/kg and the carbonate concentration is a tenth of that. The sort of buffer that one would use in the lab would have at least 10 times the bicarbonate and 100 times the carbonate. So although seawater is buffered, it is very poorly buffered.
Carbonate sediments add greatly to the buffering capacity of the ocean, which is why high CO2 levels in the distant past did not produce acidic oceans. But that is only effective on very long time scales – at least thousands of years, if not much longer. So that will be of no use in buffering the ocean against a big CO2 increase on a time scale of a century.

Reply to  Mike M.
December 31, 2014 2:02 am

So although seawater is buffered, it is very poorly buffered.

Similarly, carbon dioxide is a very weak acid even in distilled water.
Normal rainwater pH is below 7 provided that hardness remains below 1. http://pages.uoregon.edu/hof/S01havestingrain/data.html. Freshwater hardness remains usually below 1200 ppm, but tapwater pH goes above 7 also elsewhere http://water.usgs.gov/owq/hardness-alkalinity.html#chart.
Ocean hardness is above 6000 ppm and pH above 8. http://www.tvdsb.ca/uploads/ScienceProbeware/totalwaterhardness.pdf. Sounds like to a powerful enough buffer to me.
I wish alarmists good luck with the project of filling our oceans with normal rainwater.

Crispin in Waterloo
Reply to  Mike M.
December 31, 2014 8:38 am

Mike M
I didn’t seen you make any mention in your analysis of living organisms in the ocean – just the chemistry. As the organisms have a powerful influence on time scales of weeks, not 1000 years, I suspect the buffering is much larger than you infer.
There are many areas of the ocean that are short of one or two minerals so biota are limited by that. Iron is a common deficit. There are several ‘buffers’ that are not able to function now because of a lack of CO2. There is a paper on buffers including one that is still non-functional (several papers actually) focusing on the main ‘El Nino area’ off the coast of South America. The ocean does not act like a beaker of solution. It is filled with life that needs and sequesters CO2.
Personally I doubt the ocean, under any conceivable scenario, could be neutralized. As one commenter said a few days ago, the oceans will not become acidic until the planet runs out of rocks.

Reply to  Gail Combs
December 31, 2014 6:44 am

Gail, Segalstad and Jaworowski as reference is a weak shot, to say the least…
Seawater is a weak buffer, not a strong one. A 30% increase of CO2 in the atmosphere over 160 years gives a 3% increase of carbon (DIC) in the ocean surface and that gives a pH drop of 0.1 unit.
Hardly measurable with the old equipment, accurate to 0.1 pH unit and zero influence on fish and other creatures in the oceans. The pH drop is mostly near the surface, as the exchange with the deep oceans is very slow. But is measured since 1984 (-0.04 pH unit) with more accurate equipment and calculated from other variables…

Leonard Weinstein
Reply to  Ferdinand Engelbeen
January 1, 2015 6:47 am

Ferdinand, you continually refer to the poor accuracy of old pH equipment, which is only accurate to o.1 pH unit, and is trying to detect 0.1 pH change. Yet the claims of global warming are based mainly on thermometers that are accurate or read out with resolution of 1 degree C or more, and at locations that are several degrees C different from nearby locations. The total global change is less than 0.8 C over the last 150 years. Do you believe the thermometer data set, but not the pH meter set, and why?

Reply to  Ferdinand Engelbeen
January 4, 2015 1:01 am

Leonard, I have the same doubts of the thermometer trends as of the pH trends, only the pH trends are even worse as that aren’t even fixed places…
I suppose that the satellite measurements are a lot more reliable as these scan most of the surface and don’t have problems like UHI effects. The same for the more recent pH measurements as these are at fixed places and better equipment…

Aussiebear
December 30, 2014 4:20 pm

Just curious. What is with the longitudinal sampling artefacts?

Aussiebear
Reply to  Willis Eschenbach
December 30, 2014 5:44 pm

Willis,
Thanks for that! As you have spent a far amount of time off-shore I accept that explanation, that now makes sense. I like that from your estimation they would be indicative of oceanographic ships. There is an obvious intention there.

Jeff F
December 30, 2014 4:27 pm

I’m confused, we went from, “a startling data omission that eclipses even the so-called climategate event,” to, “So … was there “pHraud” in not utilizing this data? I say no, there was no fraud.”???

Hugh
Reply to  Jeff F
December 30, 2014 11:02 pm

‘we’ did’t go, it was Marita Noon’s blog based on Wallace and Willis E. disagrees to some extent.

December 30, 2014 4:32 pm

Corals evolved in the Cambrian Era with atmospheric CO2 20X higher than at present. The oceans are buffered by alkali rock. Claims that CO2 is significantly lowering pH are utter nonsense.

Latitude
Reply to  stevengoddard
December 30, 2014 4:40 pm

thus the definition of supersaturated…..
As you add an acid…more buffer comes into solution
Like Gail said…you can’t lower pH until you deplete the buffer…..and that would mean dissolving the entire sea floor..and ignoring the fact that CO2 + plankton/cyano = buffer

Reply to  stevengoddard
December 31, 2014 6:56 am

CO2 exchanges are mostly in the upper 200 m of the oceans, as that is where most of the fast exchanges with the atmosphere is. Most carbonate rock is deeper and takes more time to dissolve… the pH change of ~0.04 unit is measured at a lot of places sine 1984…

Latitude
Reply to  Ferdinand Engelbeen
December 31, 2014 8:23 am

Ferd, you need to learn where that carbonate comes from……..

Duster
Reply to  stevengoddard
December 31, 2014 6:56 pm

Corals evolved in the Cambrian Era with atmospheric CO2 20X higher than at present. The oceans are buffered by alkali rock.
Thus Gail’s point about basalt. Though you can’t discard the mantling of the sea floor by both biological and mineral accumulations which would likely run either considerably more neutral or even slightly acidic.

Dave
December 30, 2014 4:33 pm

Pathetic sampling for large portions of the oceans. Just like ocean temperature we have no accurate historical data.
Doesn’t phase those positing catastrophe.

cd
Reply to  Dave
December 30, 2014 4:53 pm

Dave
Most geoscience projects have these problems. In the oil and mining industries data is commonly sparsely and irregularly sampled (both in time and space). Statistical methodologies have been developed to deal with these exact issues. Even with regular and well sampled observations the issues similar issues still exist.

Dave
Reply to  cd
December 30, 2014 5:58 pm

The devil is in the details. What assumptions accompany the statistical adjustments, what lines of linear interpolation, what allowances for biological processes, tempurature and ocean circulation?
These can be varied a substantial amount and still meet the objectives of the scientists doing the work. It’s not good data, not good enough to justify the alarm bells.

David A
Reply to  Dave
January 1, 2015 4:46 am

Dave says…” It’s not good data, not good enough to justify the alarm bells.”
=============================================================
Indeed! Not only is the measured result, even given the best methods, inadequate, but just like in CAGW, the “C” is simply MIA. There are many studies documented at CO2 science which well demonstrate BENEFITS of CO2 in the oceans, and others that show that the theorized harms will not happen!
I note that Ferdinand is consistent in NOT advocating any claimed disastrous harms from the very minor PH changes. I also note the quality of responses to him, and consider this to be a very good example of scientists doing real science, a form of online public peer review.
One of the points Ferdinand makes is that the entire ocean is only in play over long time periods. I would like to suggest that the greater the potential change in the upper 200 meters manifests, the stronger the buffering influence of lower depts. of oceans would occur. n other words, I do not think the buffering affect of the lower depths is linear, just as the greater the increase of surface T manifests, the more lower upwelling o un-warmed water would counter the T increase.
Also, in addition to the many legitimate concerns with any and all attempts (even using the best equipment) to measure the global oceans PH flux, a think not only the date of measurements is critical, but the time of day is critical, as local PH flux daily in many areas is large. Also perhaps poorly considered is decadal changes in ocean currents and disparate ENSO conditions. Those two factors, in conjunction with the massive size of the oceans surface and their DEPTHS, widens the error bars to all the different attempts to measure ocean PH changes.
At any rate, to not even mention the two plus million prior readings, and to intermix modeled results with actual data without clearly noting the difference to political decision makers, is in my view not excusable.

cd
December 30, 2014 4:43 pm

And unless the sampling is uniform in time and space, this is a Very Bad Idea

Why? You can only work with what you’ve got. In most areas of engineering and science this is exactly the situation you have to deal with.

you can see from these maps that we cannot simply put all of that data into a single box and extract a timeline from it

Why not you could simply grid them using kriging for each year to achieve a global estimate (alternatively simple declustering method using Veronoi-type methods). Then from each yearly estimate you can construct a time series. Kriging has added bonus of supplying kriging variances as proxy to confidence.
Both suggested methods implicitly deal with data clustering. Of course there are nuances that may need to be addressed (such as choice of kriging method, whether to work in polar or Cartesian domains etc.) but these are always considerations. The temporal issue is not such an issue if you’re modelling a global summary statistic as long as the experimental approach is constant.
[Fixed italics/blockquotes. .mod]

December 30, 2014 5:04 pm

OK, an engineer’s question about the scale of all this. Atmospheric mass is ~5.15×10^18 kg. The mass of all of the CO2 currently in our atmosphere is around 2.0×10^15 kg. Mass of the oceans is somewhere around 1.4×10^21 kg. If we dissolve every single bit of atmospheric CO2 into the oceans that’s a change of a little over 1.4 ppm. Chemists, how acidic would 1.4 milligrams dissolved CO2 make one liter of sea water? (or 1 mole of CO2 in 32,428 liters of water.)
Am I missing something here besides the buffering?

Robert of Ottawa
Reply to  nielszoo
December 30, 2014 5:43 pm

If we dissolved every bit of atmospheric CO2 into the oceans, we would all, every living creature on the planet, be dead, extinct.
But there hides the Warmistas’ biggest lie – more CO2 is beneficial.

Reply to  Robert of Ottawa
December 31, 2014 4:36 am

Yea, that was my point… considering that we’ve only got about 140 ppmv “extra” CO2 in the atmosphere before we hit that point below which plants start suffering.

Duster
Reply to  Robert of Ottawa
December 31, 2014 7:43 pm

If you consider the fact that greenhouse operators add CO2 to the interior atmosphere now, then it is highly likely that plants are already suffering. When you consider the amount of primary productivity that dinosaurs required, and that the planet currently could not support a population dinosaurs comparable to the Jurassic or Cretaceous, it seems pretty certain. My favorite speculation is that the similarity between the present and the late Permian might mean the same termination. Since the end of the Permian was cold (like now in fact) and CO2 was very low (not quite as low as the present), there seems to a reasonable possibility that inadequate primary production ended the Paleozoic and ushered in the Mesozoic. So, we are experiencing a “wave of extinctions” they say. What comes after Cenozoic, and is human CO2 output slowing the onset?

Reply to  Robert of Ottawa
January 1, 2015 6:18 am

Duster, If I remember correctly the O2 levels rose throughout the Mesozoic as well. All that evil plant life gorging itself on that excess planet killing CO2. Dinosaur’s size increased along that same time line. Simple correlations but does certainly suggest that CO2 is good for life and not bad. Wonder why the Climateers can’t get their heads around that concept?

Mike M.
Reply to  nielszoo
December 30, 2014 7:14 pm

“Chemists, how acidic would 1.4 milligrams dissolved CO2 make one liter of sea water? (or 1 mole of CO2 in 32,428 liters of water.)”
That amounts to an increase in dissolved inorganic carbon (DIC) of about 0.031 mmol/kg, which would lower the pH by about 0.06 pH units.
What you are missing is that the oceans mix very slowly, so the emitted CO2 that has dissolved in the ocean is mostly in a very small fraction of the ocean volume. The estimated change in mixed layer DIC since pre-industrial times is 0.056 mmol/kg, producing a calculated pH change of 0.11 pH unit. Double CO2 would increase DIC by a further 0.064 mmol/kg and triple CO2 would add 0.054 mmol/kg beyond that. The corresponding pH increments are 0.14 and 0.15 pH unit. With triple CO2, carbonate in the mixed layer would be just over half its pre-industrial concentration.
At some point, cranking up CO2 will be a problem. Personally, I am skeptical about that happening soon.
My source for the numbers is:
Kleypas, J.A., R.A. Feely, V.J. Fabry, C. Langdon, C.L. Sabine, and L.L. Robbins, 2006. Impacts of Ocean Acid- ification on Coral Reefs and Other Marine Calcifiers: A Guide for Future Research, report of a workshop held 18–20 April 2005, St. Petersburg, FL, sponsored by NSF, NOAA, and the U.S. Geological Survey, 88 pp.
Although I downloaded it from the web some years ago, I no longer have the link.

Reply to  Mike M.
December 31, 2014 9:35 am

OK, so starting with a clean “back of the envelope” and looking at the whole of man’s contribution to CO2 instantly dissolved in the mixed layer the numbers are close to the same. Consider mixed layer average of 150m (throwing out the < 50m warm shallows and the 1000m deep near freezing polar zones) that’s 5.415×10^19 kg for water mass. Man’s contribution to atmospheric CO2 is 9.05×10^13 kg (with proper mass fraction values, my previous math was based on volume fraction… oops.) That’s still only 1.67 mg/kg CO2 in sea water or 0.038 mmol/kg. (I also used 1kg/l so I’m ignoring everything else in sea water mass wise.)
That still doesn’t make for a pH change that gets outside the real working differences of current pH meters and standard calibration solutions. And I’m assuming all the CO2 goes in at once and is 100% mixed. I’m not real worried about this.

David A
Reply to  Mike M.
January 1, 2015 4:51 am

I would like to suggest that the greater the potential change in the PH of the upper 200 meters manifests, the stronger the buffering influence of lower depths. of oceans would occur. In other words, I do not think the buffering affect of the lower depths is linear, just as the greater the increase of surface T manifests, the more lower upwelling of un-warmed water would counter the T increase

Reply to  nielszoo
December 31, 2014 7:03 am

Not a matter of quantities, a matter of pressure differences and equilibria:
– a 30% CO2 increase in the atmosphere for a certain water temperature gives a 30% increase of free CO2 (gas) in the oceans surface (Henry’s law).
– a 30% increase of free CO2 in the ocean surface gives a 3% increase in total carbon (DIC) in the ocean’s surface (chemical equilibria).
– a 3% increase in DIC gives a pH drop of 0.1 unit in the ocean surface.
Change is mostly in the surface (0-200 m) as the deeper oceans show much less exchange…

James Harlock
Reply to  Ferdinand Engelbeen
December 31, 2014 10:28 am

Very nice, but one question; with a ~30% supposed increase in CO2 in-atmosphere yielding a ~3% increase in DIC, what is the calculated increase in Biomass? Oh, you don’t have that? So much for organic equilibrium.

Bill Illis
Reply to  Ferdinand Engelbeen
December 31, 2014 11:27 am

CO2 was as high as 7,069 ppm 520 Mya and 12,000 ppm at 635 Mya.
That is 253% and 428% higher than the pre-industrial equilibrium.
So your math Ferdinand, provides for ocean pH’s of 5.4 and 3.4 respectively for the periods just when complex life was evolving.
On the other hand, many life-forms have pH’s in that range.
I think we need a new formula. Those numbers do not sound right.

Bill Illis
Reply to  Ferdinand Engelbeen
December 31, 2014 12:51 pm

Sorry, I did the math wrong. Obviously, with CO2 that high, pH goes below Zero making the ocean the most acidic substance in the universe at those periods.
New formula time.

Reply to  Ferdinand Engelbeen
December 31, 2014 2:45 pm

James,
The 30% increase of CO2 in the atmosphere has some influence: the earth is greening with 1 GtC/year or 10% of the human emissions, as CO2 is one of the limiting factors for land plant growth.
The 3% increase in DIC in the ocean surface has hardly any influence on bio-life in the oceans as CO2 (as bicarbonate) is not the limiting factor for algae growth. The summer/winter difference at Bermuda is not more than 2,5% of DIC. Trace elements like iron are the main limiting factors…

Reply to  Ferdinand Engelbeen
December 31, 2014 2:54 pm

Bill Illis, you forget that Ca and Mg were also far more abundant in the oceans… Meanwhile lots of the combination can be found as carbonates in the white cliffs of Dover (UK), the Dolomites (Italy), the karst landscapes of Ireland, the caves of Carlsbad (USA) and many other places…
But there are several web sites where you can calculate the (theoretical) pH and other ocean related data for any more recent period on earth, including ice ages:
http://biocycle.atmos.colostate.edu/shiny/carbonate/

Mike M.
Reply to  Ferdinand Engelbeen
January 1, 2015 9:45 am

Willis,
For the ocean as a whole, alkalinity and salinity are essentially constant on a time scale of centuries. There may well be small local variations. I plan to have some fun looking at the data you provided.
Bill Illis,
On geological time scales, alkalinity (and perhaps also salinity) will not be constant. Alkalinity is the total capacity of a solution to neutralize acid. For the oceans, that means that
alkalinity = [HCO3-] + 2*[CO3=] + minor bases (such as borate and phosphate)
A more acidic ocean will cause sediments, especially CaCO3, to dissolve. More CO2 in the air means more acidic rain which would increase the weathering of rocks. On geological times scales, that will raise the alkalinity and counteract the effect of higher CO2 partial pressure on the pH of the ocean.
Past episodes of high CO2 occurred slowly compared to what we are doing. I would not be surprised if raising CO2 30 times in a million years would have less effect on ocean pH than raising CO2 by a factor of 3 in 100 years.

Reply to  Ferdinand Engelbeen
January 1, 2015 3:18 pm

Willis, the real uptake depends of temperature and Revelle (buffer) factor, the increase over the past decades at several places can be seen at:
http://www.tos.org/oceanography/archive/27-1_bates.pdf
Fig. 3 and Table 2 show the trends and figures.

Mike M.
Reply to  Ferdinand Engelbeen
January 1, 2015 5:38 pm

Willis,
You will notice that in the data set there is a column labelled DIC and another labelled nDIC. The latter has some sort of salinity correction. The P_CO2 values in the file change by 13% and the nDIC changes by 1.3%, right in line with Ferdinand’s numbers.
Salinity and alkalinity have a slight upward trends, I don’t know why. The salinity corrected alkalinity, nTA, is almost perfectly constant.
I found it interesting that the file has two independent determinations of pH: a direct measurement and indirect from bicarbonate and carbonate. The r.m.s. difference is 0.007 pH unit, so if the two methods are equally accurate, the standard deviation of each is 0.005 pH unit. Impressive.

Mike M.
Reply to  Ferdinand Engelbeen
January 2, 2015 8:47 am

“Salinity and alkalinity have a slight upward trends, I don’t know why. ”
Surface salinity varies from place to place in the ocean depending on the balance between evaporation and precipitation; excess evaporation leads to higher salinity, excess precipitation leads to lower salinity. If a given location in the ocean has a trend in the relative amount of precipitation and evaporation (whatever the cause of climate change), there will be a trend in surface salinity.
The ratio between alkalinity and salinity stays constant, since all salts are affected equally by dilution. So the trend in DIC has two components, one due to a trend in alkalinity linked to the salinity trend and one due to increased CO2. The variable nDIC has the first contribution removed.

December 30, 2014 5:23 pm

The data selection is a major part of the story. What is as important, is Sabine’s reaction to questions put to him through FOI and the answers he gave. They appear to suggest they knew they were cherry picking data, but didn’t think they would get caught.

mpainter
Reply to  Tim Ball
December 30, 2014 5:43 pm

FOI? Did Sabine provide documents under FOI?

Reply to  Tim Ball
December 31, 2014 7:05 am

Tim, if you have sparse data, scattered in place and seasons over the years with an accuracy of 0.1 pH unit, how do you find a trend of 0.05 pH unit over the period 1850-1984?

Catcracking
Reply to  Ferdinand Engelbeen
December 31, 2014 10:28 am

It’s a lot more than a single tree to fabricate a hockey stick for the IPCC.
Why did they not reply to the FOI request and give snarkey replies if they had a good scientific basis?

Leonard Weinstein
Reply to  Ferdinand Engelbeen
January 1, 2015 6:59 am

If the accuracy of 0.1 pH is a random error, large data set averages are more accurate. This is exactly the same issue as thermometer reading, where plus or minus 1 degree readings (and even large offsets due to urban heating or poor placement) were used to generate a data set claimed accurate to 0.05 C or so, with a total rise in 150 years of 0.75 C. Unless there is a shifting bias in the readings that is not corrected for, your argument falls on its face.

Reply to  Ferdinand Engelbeen
January 1, 2015 2:34 pm

Leonard, agreed, but Berényi Péter has gridded the pH data in 5×5 degree boxes and he finds an essentially zero trend with an error margin over 30 years of ~0.02 unit/decade.
The measured (and theoretical) trend at a few places with modern equipment is around -0.015 unit/decade, thus not measurable with the pH glass electrode pH measurements.
The measurements in earlier decades were even more scarce and the trend smaller (CO2 increase 1850-1984 was about the same as 1984-current).

angech2014
December 30, 2014 5:26 pm

“However, it is a huge scientific resource, two million plus pH samples taken by oceanographers over decades,”
I remain puzzled how a mere 2 million bits of data cannot be analyzed in a short space of time by any of the groups with big computers.The new supercomputers in England could knock it over in 2 minutes, Mosher and Zeke 1/2 an hour, Nick Stokes or McIntyre perhaps a week.
Heck it could be a class project at any US university course on climate change.

Dave
Reply to  angech2014
December 30, 2014 6:05 pm

Data entry….
Analysis by computer is a snap, you try entering 2 million results with coordinates.

tty
Reply to  Dave
December 31, 2014 1:52 am

They are already available with dates, depth and coordinates. Or did you think Willy keyed in 200,000 datapoints by hand the last few days?

Robert of Ottawa
December 30, 2014 5:40 pm

Willis, regarding sampling density, I enquire as to why folks were measuring ocean Ph. I figure that there was local concern about the effects of industrial pollution on the oceans, thus programs to monitor closely the Ph were part of other environmental monitoring projects.
Japan, Baltic, Caspian and Black Sea?

GregK
Reply to  Robert of Ottawa
December 30, 2014 6:38 pm

Scientific curiosity to start with [why did Darwin look at finches ?], because you can and because it’s a feature of water that can measured easily.
http://en.wikipedia.org/wiki/Challenger_expedition

tty
Reply to  Robert of Ottawa
December 31, 2014 2:01 am

Oceanography is important to Japanese that get a lot of their food from the sea. The Baltic, the Black and the Caspian seas are special cases which have aberrant and very variable conditions, hence interesting to study. The Baltic is brackish to almost fresh and very influenced by river runoff and occasional injections of salty water from the North Sea. The Black sea is unique (in the present) by being anoxic at depth while the Caspian is essentially a big salt lake. Incidentally, even in the deep anoxic part of the Black Sea, with a high concentration of H2S the pH does not go lower than 7.6.

December 30, 2014 6:27 pm

Just saw Fabien Cousteau diving around the Great Barrier Reef off of NE Australia. He and Philippe Cousteau keep talking about the acidification of Great Barrier Reef etc. Looking at the average values of pH taken around that area Fig 2), it looks like it is among the most alkaline (pH 8.25). I wonder if those values were taken closer to 1910 or 2013? What are the pH values there now? Has it moved closer to pH 8.19 or 8.13 (or lower) now – that info should be available? Without time of measurements it’s hard to tell what’s going on between 1910 and now.

tty
Reply to  J. Philip Peterson
December 31, 2014 2:04 am

Probably not. The symbiotic algae in corals “eat” a lot of CO2 and keep the pH high. It can touch 9.0 in late afternoon over a coral reef. Lower in the morning of course, since photosynthesis stops but respiration continues in darkness.

December 30, 2014 6:37 pm

There is no such thing as ‘an’ ocean pH. It varies diurnally, seasonally, and by ‘ocean ecosystem’ of which there are 8 in the Pacific. Swings are 1 to 1.5 annually, far more than theoretical possible AGW changes. Driven by biology, not climate. Essay Shell Games in ebook Blowing Smoke has referenced details. That is why we exist on a blue planet suffused by oxygen.

Louis
Reply to  Rud Istvan
December 30, 2014 8:11 pm

There is no such thing as ‘an’ ocean pH.

Can I assume then that you also don’t think there is such a thing as a global temperature? Temperatures also vary diurnally, seasonally, by latitude, by altitude, and for all sorts of other reasons. Perhaps you should let climate scientists know about the futility of their efforts before they make a fool of themselves. 🙂

Reply to  Louis
December 30, 2014 11:21 pm

Of course there is no such thing as a global temperature. Temperature is an intensive property. Climate scientists have repeatedly shown themselves to be fools (or they have an agenda).

Jeff Alberts
Reply to  Louis
December 31, 2014 8:00 am

Of course there is no such thing as a global temperature. Temperature is an intensive property. Climate scientists have repeatedly shown themselves to be fools (or they have an agenda).

Ditto

Reply to  Louis
December 31, 2014 4:21 pm

Count The Git as a sceptic here, too. He also notes that the calculated global temperature has fallen somewhat over the decades…

richardscourtney
Reply to  Louis
January 1, 2015 1:59 am

Friends:
I, too, support phillipbratby when he writes

Of course there is no such thing as a global temperature. Temperature is an intensive property. Climate scientists have repeatedly shown themselves to be fools (or they have an agenda).

For those who have not read it, Appendix B of this discusses the various possibilities of what so-called ‘average global temperature’ may be and the implications of those possibilities.
Richard

ossqss
December 30, 2014 7:01 pm

Would the term “convenient incompetence” be appropriate?

Mike M.
December 30, 2014 7:39 pm

Willis wrote: “What I suspect has happened is that the mass and complexity of the data was too overwhelming, and so the investigators simply put it into the “Too Hard” pile. But that’s just speculation, the real reason may be entirely different.”
My guess is that the real reason includes issues with the accuracy and quality control of the data. Glass electrode data are usually not much better than +/-0.1 pH unit, and can easily be much worse if proper procedures were not followed. So one has to sort through the two million data points to try to figure out which are really reliable, and most will likely end up in the “don’t know” pile. So I think it is likely to be “too hard” combined with “too little chance of ending up with something useful”.

tty
Reply to  Mike M.
December 31, 2014 2:13 am

Actually no pH measurements are ever much better than +/-0.1 pH units since they all ultimately refer to calibrations with a chemical standard calibration fluid. These are claimed by manufacturer to be exact to 0.01, but they aren’t. Even the best brands often vary by +/-0.05.

December 30, 2014 7:46 pm

Thanks All for continuing to follow up and develop the WOD information.
I haven’t been able to post because of a technical problem. Also I haven’t wished to interfere, but at this point it seems there are many speculations that don’t match with the work I’ve produced on this nor do they match with the full history of my communications with the two PMEL authors.
Anthony Watts now has a copy of my transcript of PMEL communicaitons. Stephen McIntyre was given that transcript over a year ago if I’m not mistaken. Perhaps one of them will post. I don’t want that on my own site. Also all readers and writers may wish to examine the 11 posts regarding my own preliminary data extractions at
http://www.abeqas.com/category/ocean-ph/
Also it might be of interest to know that I covered these same concerns via several comments I posted at RealClimate last January (17?).. about a year ago. For some reason, there was no followup interest from anyone, but the comments are for the most part still there. Michael Mann was the guest host for that piece titled “if you see something, say something”. I’m grateful that they did not remove those comments but I hope they will sign the petition.
Also please note that the petition I produced was in response to indifference from every single subject matter expert and Senator that I took this up with discretely over many months. The petition only asks that NOAA do its job and develop this data properly. This way people like myself, Willils, and others, don’t need to take time out of our priorities to do their job for them.
Also, the petition doesn’t accuse anyone of fraud. If the PMEL authors of note were to sign the petition, that would be a good start towards reducing the heat on this topic and moving towards reform. Again the petitiion is at:
http://www.ipetitions.com/petition/restore-the-worlds-ocean-ph-measurements

trafamadore
December 30, 2014 7:56 pm

“Willis Eschenbach tips me to a story by Marita Noon, titled:
What if Obama’s climate change policies are based on pHraud?”
So now, a week later, not a fraud? If anyone is a fraud, I’m suggesting a particular grad student and his mentor both whom don’t vet their work before accusing people of fraud.

trafamadore
Reply to  Willis Eschenbach
December 30, 2014 9:09 pm

What part of “Willis Eschenbach tips me” are you try to evade?

Streetcred
Reply to  trafamadore
December 31, 2014 12:45 am

Do you have a problem with reading and comprehension ? Look at the comment from Mike Wallace at 7:46 pm … the very one prior to and, yeah, 10 minutes before your diatribe.

Streetcred
Reply to  Streetcred
December 31, 2014 4:57 pm

Follow the indentations, Willis. Had Trafamadore taken 30 minutes to compose and publish that rubbish then he/she/it definitely has an issue with reading and comprehension, so your explanation is in his/her/its case is weak. If Trafamadore had done any research into sourcing the original article alerting the pH issue then he/she/it would be fully aware that the author has been 100% ethical in how he has prosecuted his business. It is appalling that Trafamadore should accuse Mike Wallace “and his mentor both whom don’t vet their work before accusing people of fraud” … what does he think that they are, CAGW warmista?

Streetcred
Reply to  Streetcred
December 31, 2014 5:04 pm

Willis … “So sue me …” What an outrageous statement, are you serious or is it just the New Year cheer?

Streetcred
Reply to  Willis Eschenbach
January 1, 2015 10:08 pm

“So sue us all, I guess … ”
That is so immature … on what grounds do you suggest that this might be possible ?

David A
Reply to  trafamadore
January 1, 2015 5:07 am

An excellent post ten minutes before yours, directly above yours, and you poison the well with this “acidic” comment?

December 30, 2014 8:35 pm

Yes well. Readers shouldn’t HAVE to trawl through data to construct time series where prima facie an interesting scientific truth emerged from recent analysis showing a rising pH.
We spend literally $trillions. And if ocean acidification is disproven, that may be one of the most valuable discoveries in history.

trafamadore
Reply to  Andrew
December 30, 2014 8:51 pm

What are you thinking? It’s simple physical and general chemistry. The partial pressure of CO2 goes up in the air (physical chemistry), more CO2 goes into the H2O (physical chemistry), the pH falls (general chemistry). Lot’s of details, like the temp of the water and the buffering in the water (both general chemistry) and where the water comes from (history, just kidding, Ill go with physics), but in the end it’s simple physical and general chemistry.

Latimer Alder
Reply to  trafamadore
January 1, 2015 12:39 am

@trafamadore
You’re right – up to a point. You’ve written the first chapter of the story
If you did the experiment in the lab with pure water and CO2, you’d get the results you describe. That’s about as far as the theories of physical and general chemistry will take you.
But the oceans ain’t the lab and sea water ain’t pure.
The challenge for the experimentalists/observationalists is to show whether the expected effect actually happens in practice in the oceans where a whole host of other factors are in play (some of which you have mentioned).
The discussion to date show that they are nowhere near having enough usable real world data to adjudicate one way or another on the issue. Looks like they won’t have for a very long time either.
And even if there were shown to be a real world change in pH, it would be necessary to show that this actually mattered to anything we care about.
Personally I find it hard to believe that many organism couldn’t withstand a pH change of about 0.1 units. Any more than there are many which can’t cope with the temperature changes between winter and summer or between a week of low relative humidity and a week of high. Anything so highly adapted to a very narrow environmental range is unlikely to be widespread nor long lived (in evolutionary terms).

Reply to  Andrew
December 31, 2014 7:13 am

Andrew, there was no rising pH. The pH “trend” in the compilation of Wallace is the result of scarce data taken at different places and seasons over the years…

old44
December 30, 2014 9:09 pm

Strange, with all the talk of ocean acidity destroying coral reefs, no samples taken on the lower half of The Great Barrier Reef where all the fertiliser from agriculture and where the coal exporting ports are located, and very few from Mackay upwards, the same for Ningaloo Reef. it is almost like they were trying to hide something.

lee
Reply to  old44
December 31, 2014 1:49 am

‘For the period from 1940 to 2009, corals from
both inner as well as mid-shelf sites exhibit the same overall decrease in δ11B carb of 0.086 ±0.033‰ per decade, equivalent to a decline in seawater pH (pHsw) of ∼0.017 ±0.007pH units per decade. This decline is consistent with the long-term effects of ocean acidification based on estimates of CO2 uptake by surface waters due to rising atmospheric levels. We also find that compared to the mid-shelf corals, the δ11B carb
compositions for inner shelf corals subject to river discharge events, have higher and more variable values and hence higher inferred pHsw values. These higher δ11B carb values for inner-shelf corals are particularly evident during wet years, despite river waters having lower pH. The main effect of river discharge on reef-water carbonate chemistry thus appears to be from higher nutrients driving increased phytoplankton productivity, resulting in the drawdown of pCO2 and increase in pH sw.
Coral records of reef-water pH across the central Great Barrier Reef, Australia: assessing the influence of river runoff on inshore reefs
http://www.biogeosciences-discuss.net/11/11443/2014/bgd-11-11443-2014-print.pdf
Does this help?

December 30, 2014 9:38 pm

Willis: My Brother teaches “medical chemistry” at a community college in a large metro area.
Unlike my ERA when even at the University, you might have 2 to 6 students sharing ONE already 20 year old pH meter, at his school there is a pH meter for every student in the class, he intentionally gives the students one meter per 2, to enforce “teamwork”. None the less, he typically has 15 pH meters lined up, in FRESH 7.0, commercially made…buffer at the beginning of each pH usage type class. He looked at the previous measurements and comments and asked, “Who are these IDIOTS, and what experience do they have with instrumentation???”
He explained: 15 current (within 5 years) vintage, digital, self compensating (for temperature) pH meters, in commercial buffer solution. Line them all up, look at them 7.00 pH +/- 0.1 pH units. ALL THE TIME. Strangely (NOT!) you average them all and the number will be 7.0 +/- 0.07 or so pH units. It is NOT a self corrector type of error. (I.e., the central mean theory DOES NOT SEEM TO HOLD for this sort of measurement.
When he say claims to .03 or .01 pH unit accuracy by averages he SNORTED. “Meaningless”. I would tend to agree.

Mike M.
Reply to  Max Hugoson
December 31, 2014 11:38 am

I doubt it is the meter that is the issue. More likely it is the glass electrodes. If you use cheap electrodes or if they have been mishandled (banged around, allowed to dry out) it will not matter how good your meter is.
It IS possible for careful, knowledgeable workers to get precision of 0.01 pH unit with NIST primary standard buffers: R.P. Buck et al., Pure Appl. Chem., Vol. 74, No. 11, pp. 2169–2200, 2002. But it is not easy.
The problem is that it is really easy for people to think they are getting that kind of precision when they are not even close. Which is why the historical data is likely to be pretty much useless.

Auto
Reply to  Max Hugoson
January 1, 2015 12:54 pm

Max,
Many thanks.
I think your post – with many others on this thread (and many others on this excellent site) – does indicate that the science is – actually – not settled.
There is a substantial (huge?) amount we simply do not know.
The oceans are huge.
A one degree by one degree grid square is – on the equator – 3600 square (nautical) miles in extent – that is 4 767.456 016 8 square statute miles – per http://www.onlineconversion.com/area.htm (bigger than Delaware or Rhode Island, and about 85% of Connecticut, or more than half the size of New Jersey; bigger than Cyprus, and about one third the size of Belgium).
And, forgive me, most of the non-empty grid-cells have one reading for pH, during 1910 to 2013.
Well, I guess we are a bit data-deficient.
Happy New Year to All.
Auto

ferdberple
December 30, 2014 9:48 pm

took a quick look at the data:
1. most of the data is to 2 decimal places. I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.
2. I removed the outliers (ph 9), then plotted the average pH for zero depth by year, with no correction for lat long or season or girding, under the assumption that these are basically random noise by year and will cancel out.

ferdberple
Reply to  ferdberple
December 30, 2014 9:49 pm
Reply to  ferdberple
December 30, 2014 10:00 pm

ferd, what exact year is the outlier of just over 7.0?
At first glance I thought it might by 1998 which would make it both an outlier and a remarkable coincidence, but upon closer inspection it looks more like 1996 or 1997?

ferdberple
Reply to  ferdberple
December 30, 2014 10:01 pm

correction. outliers pH LT 6 or GT 9 removed
http://tinypic.com/r/2dm9vk6/8

ferdberple
Reply to  ferdberple
December 30, 2014 10:02 pm

correction for outliers here:
http://oi60.tinypic.com/2dm9vk6.jpg

ferdberple
Reply to  ferdberple
December 30, 2014 10:05 pm

the first graph didn’t have the outliers removed. the second does.
here is the SQL I used. LT and GT replaced for HTML.
SELECT OSD_All.[Year], Avg(OSD_All.[pH]) AS AvgOfpH
FROM OSD_All
WHERE ((((OSD_All.[pH])) LT 7 And ((OSD_All.[pH])) GT 9) AND ((OSD_All.Depth)=0))
GROUP BY OSD_All.[Year], OSD_All.Depth
ORDER BY OSD_All.[Year];
[See correction below. .mod]

ferdberple
Reply to  ferdberple
December 30, 2014 10:07 pm

it late, corrected sql here
SELECT OSD_All.[Year], Avg(OSD_All.[pH]) AS AvgOfpH
FROM OSD_All
WHERE ((((OSD_All.[pH])) GT 7 And ((OSD_All.[pH])) LT 9)
AND ((OSD_All.Depth)=0))
GROUP BY OSD_All.[Year], OSD_All.Depth
ORDER BY OSD_All.[Year];

Nick Stokes
Reply to  ferdberple
December 30, 2014 10:54 pm

Unweighted averaging just gives you an average of a smallish region, heavily representing, say, the area around Japan. To give an idea of the poor spatial spread of this data, I counted for each year the number of 5×5° cells that had any data in each year. There are probably 1500 or so such cells covering eligible ocean (not ice, land).

1910 1911 1912 1913 1914 1915 1916 1917 1918 1919 1920 1921 1922 1923
  10    0    3    9   17    0    0    0    0    0    0    7   15   12
1924 1925 1926 1927 1928 1929 1930 1931 1932 1933 1934 1935 1936 1937
  12   82   96   75  102  144  104  124  186  107   96   85  147   78
1938 1939 1940 1941 1942 1943 1944 1945 1946 1947 1948 1949 1950 1951
 100   53   29   37    4    6    6    7    9   50   59   59   50   30
1952 1953 1954 1955 1956 1957 1958 1959 1960 1961 1962 1963 1964 1965
  43   18   57   97  214  267  327  246  245  247  197  274  274  352
1966 1967 1968 1969 1970 1971 1972 1973 1974 1975 1976 1977 1978 1979
 259  273  331  476  446  410  491  456  425  425  503  423  352  309
1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993
 283  308  278  318  230  213  198  267  245  169  201  134   91  114
1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
  67   86   93   54   49   32   15   37   16   12   10   13   13   15
2008 2009 2010 2011 2012 2013
   9    5    5    2   19    5

In a good year, that is just 1/3 of cells. In, say, 1997, it could be about 3% coverage. And to give an idea how lopsided the data is within cells, here is, in descending order, the numbers for 1989:

259 187 163 162 157 150 125 116 112 112 112 101 83 81 80 77
75 67 66 61 59 52 51 47 44 40 40 38 37 37 36 34 32 31 27 27
27 25 24 21 20 20 19 18 18 18 18 18 17 17 17 17 16 16 16 16
15 14 14 14 13 12 12 11 11 11 11 10 10 9 9 9 8 8 8 8 8 8 8
7 7 7 7 6 6 6 6 6 6 6 6 6 5 5 5 5 5 5 5 5 5 5 4 4 4 4 4 4 3
3 3 3 3 3 3 3 3 3 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 1 1
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

That is, just 14 cells had half the data points. That’s what you get with a simple average.

Reply to  ferdberple
December 31, 2014 5:16 am

I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.
You report the reading to one more decimal place than the accuracy of the instrument. Standard lab practice.

James Harlock
Reply to  M Simon
December 31, 2014 12:16 pm

“You report the reading to one more decimal place than the accuracy of the instrument. Standard lab practice.”
On analog instrumentation? Yes. On digital? No.

Mark
Reply to  M Simon
December 31, 2014 5:05 pm

Nonsense. You usually report the reading and accuracy to the same precision. e.g 7.82 +/- 0.02

ferdberple
Reply to  M Simon
January 1, 2015 5:54 pm

I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.
==========
it appears the instrument is indeed accurate to 2 decimal places.
see: Mark January 1, 2015 at 5:19 pm
SOP 6: Determination of the pH of seawater using a glass/reference electrode cell.
9.2.2 Precision (with care) 0.003 pH units (1 SD).
9.2.3 Bias <0.004 pH units.

Mike M.
Reply to  ferdberple
December 31, 2014 11:42 am

“I find it hard to believe that scientists would record pH to 2 decimal places unless they felt their equipment had that sort of accuracy.”
Sadly, that is not true. Give people a digital readout with 2 decimal places and most will assume that they have 2 decimal places of accuracy. Really careful scientists won’t, but they are a minority.

Latimer Alder
Reply to  Mike M.
January 1, 2015 12:44 am

Surely the raw data should be captured as displayed. If others wish to ‘adjust’ it later, then at least there’s a full audit trail back to the original.
I think some guys in Norfolk (CRU UEA) got into a bit of hot water by omitting this step and just recording what they thought the instruments should have said. Bad ‘Science’.

Editor
December 30, 2014 10:18 pm

Looks like there are a significant number of gridcells or larger combinations of gridcells where well populated time series of Ph can be put together for that area. If a bunch of these show similar trends, that would seem to provide pretty good evidence about the global trend, and this approach would not be very difficult at all.
Trying to optimally extract the global PH moving average from the full pile of data might be “too hard,” but taking a good first look at it should not be.

ferdberple
Reply to  Alec Rawls
December 30, 2014 10:47 pm

you could expand the group by clause in the above sql to include location, season. this would tend to isolate the trend at each location and season, and then you could average these all together for each year. SQL NULL handling should eliminate the need for infilling as commonly required in other techniques. No need to interpolate missing data. I’ll give it a quick look in the morning to see if it makes any difference.

December 30, 2014 10:19 pm

If you put a layer where all the tectonical plates are shown above the sample’s concentration please note two important things:
Not only on the coast of Japan the Ph-samples are sampled in areas where there are frequent high techtonic activity and/or volcanos on the bottom. The activity of techtonic plates are one main reason for the sampling.
In the Baltic Sea there are two main reasons for sampling forgotten and/or not intended by those who use the usually tables for Ph-valuses:
* Due to an agreement back in time which is caused due to the problem of the Baltic Sea water being more or less poisoned the last Century, reasons all from “leaking” from industries, none or bad existing watercleaning to the number of leaking warships after WWII is one reason for a large number of samples among others taken by Naturvårdsverket in Sweden
* The water in the Baltic Sea lacks continued in-trasported normal sea water which has a higher value for Oxygen (the water in the Baltic Sea is usually said to be “brackish water”. Reason for all this can be found in one geological wellknown fact: Due to landrise still much higher north a line over from Varberg (Swedish westcoast over to close to Västervik (north Kalmar) the amount of water passing from the Baltic Sea out finally in the Atlantic Ocean, is as high as 10 000 000 000 cubic meters each year due to higher landrisespeec in the northern parts of Scandinavia (including the Baltic Sea)
South the mentioned line there is a landsinking.
This causes effects on the existing polluted sludge storage which in it self is a problem for the countries around the Baltic Sea.
All in all the places where no or only a few samples been taken are the majority of places around the world’s Sea systems….
Something to be better taken into consideration, I think….

TimTheToolMan
December 30, 2014 10:45 pm

Willis writes “There are, for example, about 400 1°x1° gridcells that have more than a hundred observations per gridcell, and groups of nearby gridcell cells combined have much more data.”
Maybe there are some grid cells that are adequately covered temporally to do a trend on? It’s only a sample but that again climatology does that all the time with proxies to get their historical global temperature trends….

Reply to  Willis Eschenbach
December 31, 2014 4:39 am

Let me be clear that regardless of what this data shows, I think that the ocean is gradually becoming more neutral, at about 0.01 pH units per decade, as a result of increasing atmospheric CO2. This is most clearly shown by the Hawaii HOT time series of pH measurements.

I’ve witnessed some diplomats bowing simultaneously and successfully to opposite directions. Scientists should also stick to their own strengths. For example, some contributors here have already convincingly demonstrated the the infinitesimally small neutralizing impact on ocean pH of all atmospheric CO2 – let alone the about 4% human portion. There is very little to add to it, but perhaps the following:
The islands of Hawaii rise up to 13,675 ft (4,168 m). Much of the Pacific Ocean surrounding the state slopes down to 20,000 ft (6,100 m) deep. It’s pretty impressive and ever on-going. It seems hasty to exclude its temporary impact on ocean alkalinity* in the region.
*Assuming that an ISO 17025 accredited laboratory is willing to declare 0.01 pH unit accuracy even for the tested samples, let alone extrapolating beyond.

whiten
Reply to  Willis Eschenbach
December 31, 2014 7:50 am

Hello Willis.
My understanding in this pH thingy is that it relates more to the climate than to the impact on life.
Of course there has being going on a much hypet noise about the danger to the life, but the main point is that it is about the climate.
The pH variation in the oceans is a significant pointer to the temp variation in the oceans.
Cherry picking a point in time and showing an oceanic temp picture for that time and then trying to imply forcefully that that must have been the case for a longer time period it does inforce a false perception and a falce (manufactured fact) proof of the oceanic temp variation, which by the way is very important to understand the climate, especilly in the last 150 years (the GW era).
The oceanic temp measurements may not give a good enough picture of the oceanic temp trend during the GW era.
The pH measurements and it’s trend may assist to a better estimation towards it.
As far as I can tell, the pH drop in oceans as served by the Feely and Sabine it implies that there has being a considerable absorbtion of CO2 from the oceans during almost all the anthropogenic CO2 emission era, meaning that the oceans were in a warming trend for all that time, as expected in a AGW scenario or a human-made GW.
The period of the significant pH drop after 1988, as per Sabine’s work, is not a long enough period to support in it’s own the claim of the “acidification” of the oceans. Actually the “acidification” (as a claim forwarded) implies (rather strongly) that even before 1988 the “picture” has been the same, a supossed significant pH drop, a warming trend for the oceans….aka AGW.
20 years is a very short time, even in the case of that sharp pH drop to reach to a conclusion that anthropogenic CO2 emissions is actually causing oceans acidification, unless implying and suggesting (rather forcefully and arbitrary) that that must be the case even prior……….and that sharp drop (as cherry-picked) means that it is good only for compensating for the time period of the “bad data”. In it’s own is good for nothing else.
As already accepted, by a very “good” reason for the cherry pick of data given……..as there was not a choice but to resolve to it.
The problem generally with “cherry-picking” of this nature is not actually the act itself, or the excuse about it one may give or offer, but actually what was done with it,…… for what purpose and for what motive…. is the real problem.
Served as a fact for gonverment policy is far to wide and long reaching……….not mentioning the whole media hype and noise……….
Sorry for going so long with this, only trying to explaing my own understanding.
cheers

Reply to  whiten
December 31, 2014 8:17 am

Hello Whiten,
If the oceans warm, they will expel CO2 and the pH will increase.
What is measured is that more CO2 is dissolved in the oceans (total carbon increases) and the pH decreases, despite the temperature increase.
So I fear that you have things somewhat in reverse…
The main problem is that the real drop in pH is only 0.04 units over the past 30 years, so you need very accurate equipment which was absent before 1980…

Latimer Alder
Reply to  Willis Eschenbach
January 1, 2015 12:49 am

@willis
Ummm.. I think the best you can say is that ‘At Hawaii, the ocean is gradually becoming more neutral’.
Generalising from just one series to ‘the ocean’ is going a lot further than the available data allows.
But I agree with your general point. Any organism so specialised that it can’t withstand a pH change of 0.1 units is going to be a very short lived one in evolutionary terms

mpainter
Reply to  Willis Eschenbach
January 1, 2015 6:35 pm

More CO2 —>more plant food—>more plants—>more organic debris—>lower pH at depth
BUT
Upwelling—>more nutrients—>proliferation of plants—>love that CO2 yum yum
win-win for the oceans

Geoff Sherrington
December 30, 2014 11:42 pm

Two short statements sum up the whole matter.
1. The glass pH electrode method has instrumental errors greater than the plausible variation in waters under test.
2. So do later methods, because of sampling problems.

Leonard Weinstein
Reply to  Geoff Sherrington
January 1, 2015 7:16 am

Geoff, so do thermometers that read out to 1 degree C and had many bad locations, have possible errors larger than the variation. These were used over 150 years to claim a 0.75 C increase with 0.01 C accuracy. However, if the variations are random, better averages can be determined if sufficient numbers of samples are used. This applies also to the pH samples.

ren
December 31, 2014 12:38 am

This declining productivity of the ocean leaves in seawater is not bound carbon dioxide, the solubility decreases to the temperature rise of the Ocean (about one degree Celsius since 1910). Excess carbon dioxide is emitted into the atmosphere and its increasing concentration in sea water results in acidification of the ocean.
Ocean productivity is decreasing due to its decreasing fertilization, ie. Decreasing supplies from the depths to the surface layer of seawater silicates, phosphates, carbonates, iron, etc. Elements determining the continuation of photosynthesis, carbon dioxide binding with seawater. Lowering the productivity of the ocean is the result of a weak fertilization. Poor content life-giving elements in surface sea water is in turn the result of cosmic processes, but let’s talk about this turn.
The ocean is a biological machine and her life depends on the mixing of water in its depths. The process is as yet poorly recognized and is now marked by a lack of knowledge about the processes of ocean water exchange. Since life in the ocean is endless, it is clear that there is a circulation of water in its volume. It is caused by the constant and variable gravitational influence of the Moon and Sun on the density of ocean waters varied. Ocean tides occur on the surface and in the depths of the sea. Dense and cold water deep sea bottom sediments containing particles (including life-giving elements and dissolved minerals), escape to the surface cooling and fertilizing it, and oxygenated water surface and sink into the depths where oxygen support biological processes. Additionally upwelling (rich in silicates, phosphates, carbonates), the surface changes its acidity by neutralizing it. Water exchange between the depths and the surface is intensified by the constant changes in the position of pole-changing inclination of the Earth’s axis. This causes a change in the centrifugal force acting on the inertial mass of water and its movement horizontally and vertically in the oceans. Changing the position of the poles are due to changes in the geographical position of the Earth’s metallic core mapped location change of the magnetic poles. The kernel of gravity moves in a fluid under the influence of external kernel variable Sun’s magnetic field. When heavy metal core inside the Earth moves the liquid outer core is a change in the position of the center of gravity of the Earth and changing the position of the axis of rotation. This results in the geographical position changes polarity and as a result takes place under the influence of a variable centrifugal force, inertial motion of ocean water and mixing them in a volume’s ocean.

Mervyn
December 31, 2014 1:26 am

Ocean acidification … the most unscientific expression used to suggest to people it is happening when it is certainly not happening at all.

Chris Wright
Reply to  Mervyn
December 31, 2014 5:20 am

Absolutely. If the consensus trend is correct, the oceans are becoming more neutral, and would have to pass through a point where the water is perfectly pure. Only after that could it be described as ‘acidic’. Currently the oceans are not acidic in any shape or form, and therefore they cannot be undergoing the process of acidification.
It seems to me that everyone is bending over not to use the word ‘fraud’. The authors decided to delete a vast amount of data, presumably without a scientific proof of this in their paper. Simply to call the data ‘unreliable’ or whatever without proof is completely unacceptable.
Of course, by cutting off the data at 1988, it is almost certain that they are giving a completely false picture. Mike Wallace’s reconstruction in the other thread shows that, despite a fall since 1988, since 1900 there is essentially no trend. ferdberple’s average from the data shown above possibly shows a positive trend over this period (becoming less ‘acidic’). It also shows a positive trend in the last few years.
If these reconstructions, however preliminary, are correct, then the result is astounding. It means that pH has been changing in a natural cycle over the last 100 years, and there is no increasing ‘acidification’ that could even remotely be linked to CO2.
It has been rightly said that ocean acidification is the last refuge of the scoundrel.
I call it more than that. I call it scientific fraud.
Chris

Reply to  Chris Wright
December 31, 2014 7:27 am

Fraud implies malicious intent. Based on the past performance innocence cannot be excluded.

Reply to  Chris Wright
December 31, 2014 7:29 am

Chris, Mike Wallace’s compilation of the data doesn’t show a global or even local pH trend. It shows the average of each year of pH measurements taken at very different places and different seasons with an equipment that can’t measure the faint change in pH caused by more CO2 in the atmosphere.
It is the same as lumping the temperature data from all station above 30N together one year and the next year mainly from stations between 30S and 30N and then conclude that the atmosphere is warming…
The modern measurements since 1984 do show a small trend of 0.04 pH units at all open ocean places and repeated ships cruises if looking at the same places and the same season over time.

johnmarshall
December 31, 2014 3:09 am

You discarded 2% of readings because they were ”outside the normal pH envelop”. But those figures are an average of the pH data not a true average of the oceans as a whole. There are regions where pH is 4-4.5 but you would have discarded those perhaps. Those discarded data must be inspected for position, date, time, and depth.

steverichards1984
December 31, 2014 5:14 am

What is needed is a ‘pH Explorer’ similar to the ‘KNMI Climate Explorer’.
Oh for the skills and time!!!!

Ed Zuiderwijk
December 31, 2014 5:28 am

Notice the sparseness of data around Antarctica.
What was that again? Increasing Antarctic ice extent because of more fresh water run off?

Gary Pearse
December 31, 2014 5:29 am

Any data on pH is of value. If we had only a couple of dozen samples of the ocean spread over all of them, we could at least say the ocean is a bit variable but it is around pH8. If we were sampling the ocean on Titan and we had only one site to select, could we not feel confident that it was a hydrocarbon sea and probably, because of the ‘hydrocarbonological cycle’ that the whole works was hydrocarbons?
I already see something interesting. The lower pHs around the continents and particularly in the polar regions – means something? Also pH does vary with temperature a little bit (but the reverse of what we see in polar waters -pH up with Temp). Also major rivers lower pH locally, probably why continent margins seem to have lower pH. Also, pH on the ocean surface would be affected by heavy rains. I like the 1metre samples better.
A lot of confounding complications. However, I think taking all samples in decade bins for 1910 until the present decade should give us a reliable enough trend to see if pH has been lowering over a century. By the way, what was the average? Let me guess….Hmmmm I’d say pH 8.

Coach Springer
December 31, 2014 5:44 am

There is a whole wing of regulation that punishes people and businesses of all sizes for misrepresentations related to omissions of material fact. This one seems pretty glaring and material. You usually don’t get the people going on record as to intent as apparently also happened here. Not as fraudulent as a hockey stick, but still possible to at least get charges filed in a different field of endeavor. Leaving large amounts of data out without addressing it prominently and in full should automatically seem reprehensible to a scientist trying to do honest science.
Even preparers of a mutual fund prospectus know you have to highlight important caveats +and prominently+ in order to not be misleading. Using selected data that raises an alarm seems no different than using selected data that exaggerates investment performance. Not to mention the pretense of prediction that accompanies every press release if not every “study”

December 31, 2014 6:52 am

Willis, I’m sure you have this under control already but I think this is interesting. If we look at the number of measurements by year we see that after year 2000 we essentially have the same low frequency as in the 1930s. There is huge drop off after 1990. I haven’t look at how this affects the different grid cells, I can only assume that the coverage is still the same but redundant measurements in nearby areas are no longer done to the same extent. So possibly, your coverage graph may be sligthly missleading.

ferdberple
December 31, 2014 7:06 am

here is a plot of the raw data, between pH 0 and 14. As can be seen there is a likely data quality problem in the mid 1990’s that would likely skew any trend to show “acidification”. There is also a similar problem in around 1960.
http://oi60.tinypic.com/21do9qd.jpg

ferdberple
Reply to  ferdberple
December 31, 2014 7:13 am

As for a trend, looking at the graph of raw data immediately above, the mark 1 eyeball says there is no significant trend likely to be found in the data. It looks pretty much flat line from 1910 to present. pH starts slightly above 8, and ends slightly above 8, and doesn’t show any significant pattern trend above or below the line.
Yes if you correct for location, season, and sample density you may be able to narrow the spread of the data and find a trend, but there is also a good chance of introducing a spurious trend.

Reply to  ferdberple
December 31, 2014 7:38 am

Ferd, the theoretical trend from increased CO2 levels is 0.1 pH unit since 1850, of which 0.04 pH unit since 1984. You have definitely proven that the glass electrode pH measurements are too inaccurate to show any trend in any direction. Thus the answer of Sabine was right: insufficient quality of the data.
Except if you can combine samples at the same place and season over time, but even then…

ferdberple
Reply to  ferdberple
December 31, 2014 7:48 am

Ferdinand by your logic the glass thermometers used to create a statistical record of average surface temperatures cannot work either.
However, that is not correct, because statistics can be used to combine many inaccurate samples into 1 sample of greater accuracy.
What I’m seeing that the underlying data has no trend, because the trend = 0, not because the equipment is inaccurate, but because the data shows that acidification is not happening.
Thus, the data shows that the theory that human activity is acidifying the oceans is contradicted by the data.

Reply to  ferdberple
December 31, 2014 8:14 am

Fred
Not so. Whilst a stastically meaningful result can be gained where, for instance, there have been seven readings of a thermometer at the same place and the same time, by discounting the outliers and averaging the rest, in reality that doesn’t happen as there is often just one reading. No matter how much you massage it, should it turn out to be inaccurate,, a bad reading is a bad reading .
The same applies to ph readings. If numerous ones were carried out in one place at the same time I would accept you can extract meaningful data from it. However, I suspect these are highly random readings and their value in part, if not in total needs to be queried.
Tonyb

Reply to  ferdberple
December 31, 2014 8:24 am

Tony,
It is even worse for the pH readings: the samples are not even taken at the same place and in the same season… That can give differences of up to 1 pH unit from one year to the next, depending of where and when the weight of the samples was in each year. While one is looking for a trend of 0.1 unit over 160 years…

Reply to  ferdberple
December 31, 2014 9:39 am

Ferdinand
I can not see how these can give any sort of meaningful data unless some very specific places are selected where the methodology and sample numbers can be shown to be meaningful.
Tonyb

December 31, 2014 7:13 am

Nicely done Ferdberple (and others). I think your independently developed time series is consistent with my plot which has been featured in Anthony’s first post on this topic, given that your plot covers all records and that particular plot of mine filtered out all records from depths greater than 200m.

ferdberple
December 31, 2014 7:39 am

My conclusion looking at the data is that the explanation that it is not of sufficient quality to calculate a pH trend is without foundation:
To the degree that the pH readings are “random” as to location and season from year to year, and the underlying data is bound by the central limit theorem, it can be argued that these readings are simply random samples from a population, and will be normally distributed around the mean for that year, and can be treated as such statistically.
While the above is unlikely to be strictly true, because weather, human populations and geography will favor some areas; weather, population and geography themselves are essentially random.
There is a danger that gridding and infilling will simply create false trends where no trends exist, because it will give significance to areas where data is sparse, and remove significance from areas where data is plentiful.
If there is a real trend in the data, it should be somewhat visible to the eye in the raw data without the need to torture the data to gain a confession. I’m not seeing any sort of trend in the raw data.
I do think however that the data shows more than enough data quality to calculate pH trend (or lack of trend), as aside from some obvious data quality problems, the data shows reasonably tight grouping. It isn’t scattered all over the place as it would be if it was low quality and/or high noise.
Thus, my conclusion looking at the data is that the explanation that it is not of sufficient quality is without foundation.

whiten
Reply to  ferdberple
December 31, 2014 8:45 am

ferdberple.
You do not get it do you! 🙂
The data that do not support or comply with the theory is not good data, or as they say lately is of no sufficient quality.
There is no buts and ifs there……… theory first then data but only if data supports the theory otherwise it becomes junk data….or worse it gets lost and destroyed in the process of the hockey-sticks and cherry-picking .:-)
I think you have already heard and know about the 97% consensus and the 95% certainty on the theory, whatever theory that is….:-)
The latest and improved modern-day climatology. 🙂
Ferdinand has being telling you that for some time now.
cheers

Reply to  ferdberple
December 31, 2014 9:10 am

Ferd, as far as I remember from very long ago statistics, you can obtain meaningful results if the sampling is representative for the whole population. In this case there is a huge oversampling in 10% of the areas and near no samples from other areas.
That is as representative as looking for the average height of people on earth where your sample is 50% composed of people from Scandinavia and the rest scattered over the earth and practically none from South America and Asia…
All what one can do is looking at binned data within one small area and the same seasons and look at the individual trend at that area. Eventually combining them by removing the local and seasonal offset.
shows more than enough data quality to calculate pH trend
Sorry, even after throwing out the worst outliers, the whole cloud is between pH 7 and pH 9. Accurate measurements (colorimetric and calculated) since 1984 show a seasonal variation of 0.05 pH unit (Hawaii) up to 0.1 pH unit (Bermuda). Trend in several places: ~0.04 unit.
Are you really sure that the glass electrode data are accurate enough to show such a trend?

Duster
Reply to  ferdberple
December 31, 2014 8:10 pm

I would question that the readings are necessarily random by season. They might be over much of the planet, but both the arctic and Southern oceans can get right cranky as you move into winter. There’s a reason that many field scientists talk about “field season,” and it is all about climate. This may in part explain the sparsish data around Antarctica.

KNR
December 31, 2014 8:12 am

‘two million plus pH samples taken by oceanographers over decades’
Sounds like a lot but lets us look at that again , its over decades so it reality even an yearly average for limited area not be possible and the ocean is two thirds of the planet with some areas having no or little coverage . so the actual amount of coverage for any area is actual not much. And the old trick of ‘smearing’ the data over a large area is hardly one that can be accepted without question.
The problem remains the data is used not because its know to be a good representation of what is being measured , but be because its ‘better than nothing ‘ So in one way not using can have a degree of justification, the trouble is they replaced it with worse model run ‘data’ with all the problems that brings and simply have not made it clear why this real world data was rejected in the first place and given the authors own backgrounds and former publications , the temptation to get the ‘right’ has opposed to a honest result can be seen has one they may well have fallen for.
Once again in climate ‘science’ we see the professionals working at a standard unacceptable for an undergraduate , the rejection of real life related data without explanation of reason. And once again we can ask , is there actually any standards in this most politicised of ‘sciences’

A C Osborn
December 31, 2014 8:26 am

My greatest take from this post and the comments so far is this by our apparent resident Oceanography expert.
“Ferdinand Engelbeen December 31, 2014 at 6:44 am
The pH drop is mostly near the surface, as the exchange with the deep oceans is very slow. But is measured since 1984 (-0.04 pH unit)”
So as with the so called “Global Temperatures” we have a POSSIBLE change over 30 years that is minute in comparison to that which the earth experiences on a daily & annual basis and which humans (and probably all sea creatures) cannot even detect.
And just like with the temperature the Warmists want to waste Trillions to offset for a Possible change of 0.12 pH unit over the next 100 years and that is only in the top 200M of the Oceans.

Reply to  A C Osborn
December 31, 2014 11:45 am

AC, where in the life of WUWT have I ever said that the minute temperature increase over the past 100 years or the 0.1 pH unit decrease will have any negative impact?
Most sea creatures (coccoliths, corals) evolved in much higher CO2 levels and temperatures.
But my stance is that you can’t lump a lot of inaccurate pH data of different places and different seasons together and call the result a “trend” of ocean pH…
As good as you can’t do that with historical CO2 data measured by wet methods in the middle of Paris or forests or temperatures in growing towns…

ferdberple
December 31, 2014 8:29 am

Here is the raw data for depth 0, with a quick cleanup for the obvious data quality problems. The trendline shows no acidification.
http://oi60.tinypic.com/9s7xvo.jpg

Reply to  ferdberple
December 31, 2014 9:18 am

Ferd, look at the data from the same places in the oceans in the same season below Japan:
http://www.data.jma.go.jp/kaiyou/english/oa/tr_pH_WINTER_137E_en.png
How many of the raw data were taken at the same place in the same season?

ferdberple
Reply to  Ferdinand Engelbeen
December 31, 2014 9:25 am

your result above for japan is a cherry pick. it is statistically insignificant.
the brute force result previous is essentially a random sample. so long as the data is bound by the central limit theorem the results should be “good enough” to at least get us in the ballpark and tell us if there is anything significant to be found.
As Berényi Péter results below confirm.

Reply to  Ferdinand Engelbeen
December 31, 2014 9:41 am

ferd, look at the difference in measurement error: +/- 0.002/decade (real equipment) vs. +/-0.038 (statistical, equipment at +/- 0.1).

ferdberple
Reply to  Ferdinand Engelbeen
December 31, 2014 10:10 am

There are a whole lot more Chinese peeing into the rivers that flow into the oceans south of Japan that there used to be. Not only is this causing the oceans to rise (biggest increase in sea levels are in that part of the world), now we have proof they are acidifying the oceans as well. Hopefully the UN will get a global agreement for everyone to stop peeing before it is too late.

ferdberple
Reply to  Ferdinand Engelbeen
January 1, 2015 9:09 am

have you stopped to think about what the graph actually shows? 3 reading, each almost 700 miles apart on the ocean, with different currents, different rates of evaporation, rainfall and photosynthesis. each with different pH but EXACTLY the same slope on the graph.
And you don’t think to question? Have you ever seen 3 experiments in science, conducted at 3 separate locations, deliver exactly the same results? Almost as though the experimenters were in communication with each other.
and then stop to ask yourself, in ocean pH is such an issue, why does life not die off every day and every year, given the change in pH due to location and season? the measurement is a nonsense, and the fact that three locations deliver the exact same result over 35 years.shows collusion.
you wouldn’t believe this result if three locations showed EXACTLY the same trend for temperature, rainfall, or any other physical measurement. you would think they were cooking the books. yet you accept if for pH to what, something like 1 part in 1 million? because to my eye that appears to be how similar the slopes are. the data is not believable.

Mark
Reply to  Ferdinand Engelbeen
January 1, 2015 5:02 pm

Wouldn’t an obvious explanation be fertilisation in coastal waters from run off? Having dived quite a bit at various world locations I can assure you that I see far more algae on reefs today than I did 30 years ago…

ferdberple
December 31, 2014 8:45 am

If anything, the trendline in the raw data shows that the surface is becoming less acidic, which would explain why the atmosphere is showing more since 1910. As CO2 has been driven out of the oceans into the atmosphere, the ocean pH is increasing, as is the CO2 ppm in the atmosphere.
So, if anything, the raw data is consistent with the theory that the increase in atmospheric CO2 is not due to human burning of fossil fuels. Rather, it represents a loss of CO2 from the oceans, due to a process that is evidently not yet well understood by science.

Reply to  ferdberple
December 31, 2014 9:27 am

Sorry, impossible: there is an increase of total carbon measured in all open oceans over time (lots more accurate measurements than pH). That is because the oceans absorb part of the increase in the atmosphere, not the other way out.
If the oceans were a net source, and humans add twice the amount as found in the atmosphere, where does the rest go? into space? Not in vegetation, as that only absorbs some 10% of human emissions (as proven by the oxygen balance).

ferdberple
Reply to  Ferdinand Engelbeen
December 31, 2014 10:14 am

History shows there is no shortage of scientists that said something was impossible – only to later be proven wrong.

Reply to  Ferdinand Engelbeen
December 31, 2014 11:56 am

Ferd,
Berényi found an overall trend of -0.002±0.038/decade for pH measurements
The Japanese found a trend for specific places of -0.015 to -0.018±0.003/decade
As far as I can see, the data of the Japanese are widely within the error margin of what Berényi found, but with much better equipment.
But you haven’t answered my question where in nature the sink is that removes halve the human emissions + all the extra CO2 alleged to come out of the oceans?

ferdberple
Reply to  Ferdinand Engelbeen
December 31, 2014 6:39 pm

where in nature the sink is that removes halve the human emissions
=================
algae. the true masters of planet earth, on which all other life depends.

Latitude
Reply to  ferdberple
December 31, 2014 10:12 am

“shows that the surface is becoming less acidic”…which is what you would expect from plankton/cyano when carbon is not as limiting

Reply to  Latitude
December 31, 2014 12:40 pm

Latitude, CO2 was never a limiting factor in the oceans, trace elements (iron) are the limiting factor.
During spring in Bermuda including algal blooms, DIC (mainly bicarbonate) drops with 2.5% in seawater. That is all.

Latitude
Reply to  Latitude
December 31, 2014 1:03 pm

….I can’t believe you just said carbon can not be limiting

Reply to  Latitude
December 31, 2014 1:42 pm

Latitude, CO2 is one of the limiting factors in the atmosphere, it is not a limiting factor in the wide oceans.
Total carbon (DIC), of which over 90% bicarbonate, the building block for most shells and corals, at Bermuda in winter/spring: 2060 μmol/kg in summer/autumn. After several algal blooms: 2030 μmol/kg. Doesn’t seem that algae are starving from bicarbonate shortage. But the change in DIC by algae has a huge influence on pH and pCO2.

Latitude
Reply to  Latitude
December 31, 2014 3:02 pm

Ferd…the higher the pH the more limiting Carbon from CO2 becomes

Nick Stokes
Reply to  Latitude
December 31, 2014 4:00 pm

Land plants can get all the CO2 they need by opening their stomata. CO2 supply is limiting when the plants have to restrict stomatal opening to limit water loss by evaporation. Not a problem for marine.

Berényi Péter
December 31, 2014 8:58 am

A preliminary look at the data shows beyond doubt, that ocean pH is decreasing indeed, at a rate of -0.002±0.038/decade. In other words, it is absolutely stable.
(5×5 deg grid boxes, monthly averages, trends computed for grid box/month combinations with at least 15 years of data – 382 such boxes were found)
If only grid boxes with at least 20 years of data are considered (204 items), ocean pH trend is -0.002±0.031/decade, therefore the null result is reasonably robust.

Reply to  Berényi Péter
December 31, 2014 9:15 am

Berényi,
Have you taken into account the season of sampling: that gives a difference of 0.05 to 0.1 pH unit, due to temperature and bio-life variability…

Berényi Péter
Reply to  Ferdinand Engelbeen
December 31, 2014 9:18 am

Yes, trends are only calculated for the same month of the year in each grid box.

Berényi Péter
Reply to  Ferdinand Engelbeen
December 31, 2014 9:29 am

I have given a try to grid box / month combinations with at least 30 years of data (81 items). The result is +0.003±0.026/decade, therefore the null result is incontrovertible.

Reply to  Ferdinand Engelbeen
December 31, 2014 12:16 pm

As the measured (and theoretical) trend in several places is about 0.013 pH unit per decade, that still is largely within the error bounds of the overall trends.
Maybe an interesting question: can you look at trend of the 20/30 years after 1989 of the grid box where more accurate measurements were done like Hawaii and Bermuda?
Bermuda was/is sampled at two places:
http://bats.bios.edu/bats_location.html
Hawaii deep ocean measurements are done at 22 45’N, 158W, 100 km north of Oahu.

Mark
Reply to  Ferdinand Engelbeen
January 1, 2015 3:14 pm

Yes, but when you average multiple samples and at the same time note temperature can you not compare readings at the same site? Did the pH electrode report proton activity or not? Or are you proposing that it is fundamentally impossible to ever measure pH to within 0.1 pH units?

ferdberple
Reply to  Berényi Péter
December 31, 2014 9:19 am

-0.002±0.038/decade
==========
that shows a very close match with the raw data brute force plot. well within the error bounds.
which is in itself interesting because it confirms that for all the gridding and infilling that is done to try and compute “global” averages, alarm bells should ring if the “corrected” result shows significant statistical difference from the raw data.

Latitude
Reply to  ferdberple
December 31, 2014 10:14 am

+1

Reply to  ferdberple
December 31, 2014 12:21 pm

And a close match with the more accurate equipment in the Japanese and fixed stations used in the past 20/30 years, well within the error bounds…

Reply to  ferdberple
December 31, 2014 12:32 pm

Ferd and Latitude,
Have a look at the original “trend” of Wallace for the past 30 years: that shows a drop of 0.3 pH units, which is widely outside the error margin per grid found by Berényi Péter.
So can we agree that the compilation by Wallace doesn’t show the real trend (whatever if that is zero or very small)?

James Harlock
Reply to  ferdberple
December 31, 2014 12:36 pm

I always love it when I see a supposed rate of change that has an error of +/- 1500-1800%. Meaningless.

Reply to  ferdberple
December 31, 2014 12:48 pm

James Harlock,
Agreed! The problem is that Ferdberple and Latitude still think that that rejects the few series where the accuracy of the measurements is much better, but still think that a “trend” with glass electrode pH measurements has a meaning…

Latitude
Reply to  ferdberple
December 31, 2014 1:01 pm

Ferdinand, You don’t know what I think

Reply to  ferdberple
December 31, 2014 1:24 pm

Latitude, agreed, one can never know what somebody else really thinks, I sometimes don’t know it from myself…
But I like to know your current thoughts about the pH “trend” compiled by Wallace and the general possibility that glass electrode measurements can show a decreasing trend in the order of 0.015 pH unit/decade over the past 30 years…

Nick Stokes
Reply to  ferdberple
December 31, 2014 4:09 pm

“I always love it when I see a supposed rate of change that has an error of +/- 1500-1800%.”
Yes. That’s what you get from the Mike Wallace data which Feely is criticised for not using. For the Hawaii data he did use, the trend was 0.0188 +- 0.0022 /decade.

Nick Stokes
Reply to  ferdberple
December 31, 2014 4:12 pm

Correctoion, the trend was -0.0188+-0.0022

ren
December 31, 2014 10:24 am

“1. Period of stabilization of the magnetic activity Sun.
2. Stabilization period earthly pole position.
3. Descending upwelling in the ocean causing a decline in their photosynthesis and warming seawater.
Reducing CO2 solubility in seawater as a result of heating surface ocean waters, reducing the absorption of CO2 in the process of photosynthesis, increase the content of CO2 gas in the surface waters of the sea due to the increased acidity, decrease absorption of CO2 from the atmosphere and gradually increasing the concentration of CO2 in the atmosphere by diffusion of excess CO2 from seawater into the atmosphere to a level of 300 ppmv over the duration of about 20 000 years Earth’s poles traffic loss and the consequent warming ocean waters about 12 ° C and warming the Earth about 12 ° C.”

Robert W Turner
December 31, 2014 11:21 am

No evidence for fraud, WHAT!? Receiving $100,000 from the Heinz foundation specifically for this research and omitting data with no explanation, I call that evidence.

Robert W Turner
Reply to  Robert W Turner
December 31, 2014 11:25 am

http://www.heinzawards.net/recipients/richard-feely
Read that and tell me what it smells like. Smells like fraud to me.

Catcracking
Reply to  Robert W Turner
December 31, 2014 4:22 pm

Robert,
Interesting claim in your link:
“…discovered the startling fact that corrosive waters were at acidic levels not predicted by climate change models to occur for decades.”
I wonder if Feely has any evidence to support the claim that the waters were at the acidic levels?
Does he believe it is accurate?

Reply to  Robert W Turner
December 31, 2014 1:00 pm

I am sure that the Heinz foundation only supports research that they like, but that doesn’t imply that what Feely, Sabine and a lot of others have done is false. Feely and others did a lot of other ocean research than pH alone.
And as Berényi Péter has shown, the margins of error from the glass electrode measurements are larger than the trend measured/calculated over the past 30 years. Thus Sabine was right to reject all old pH data made by glass electrodes, as these can’t show the (theoretical) trend…

ferdberple
Reply to  Ferdinand Engelbeen
December 31, 2014 6:44 pm

Thus Sabine was right to reject all old pH data made by glass electrodes
===================
by that logic we should also reject glass thermometer readings, which have been used to calculate a 0.6C temperature change over 100 years.

Reply to  Ferdinand Engelbeen
January 1, 2015 4:56 am

Ferdberple,
If the margins of error are larger than the trend, then it is impossible to conclude anything from the data. That does mean that the historical pH data are worthless to deduce the real (calculated) pH trend. That doesn’t mean that the data are worthless for other interesting items, as they do give some information about pH distribution over latitudes and seasons, which are much larger than the trend.
But you can’t deduce a trend like Wallace has done from these data and then accuse the researchers of “pHraud”…
I don’t know what the margins of error are for temperature readings, but as that are much more data from a lot more places, the overall error may be smaller, although other problems may arise (UHI, number of stations, change in equipment,…).

ren
December 31, 2014 11:34 am

“EPOCA was the first international research effort on ocean acidification. The 27-member consortium put many other processes likely to be affected under the microscope. These include nutrient uptake, reproduction, acid-base regulation, nitrogen fixation and primary production. Changes in the dynamics of these biological processes are likely to affect marine flora and fauna profoundly.
The four-year long project produced results based on four themes. One of the major findings under the first, ocean chemistry, is that acidification measured in terms of pH drop in the Arctic near Iceland is 50 % faster than average rates in sub-tropical zones in the Pacific.
Project researchers coupled Earth system models (ESMs), global and regional ocean models, and a sediment model to anticipate how acidification will alter ocean biogeochemistry. Climate change has little effect on acidification except in the Arctic, where freshening from ice melt exacerbates the situation. Regional model simulations highlighted the vulnerability of some near-shore regions as a result of river input and organic matter degradation as well as local upwelling systems.”
http://cordis.europa.eu/result/rcn/85717_en.html

ren
December 31, 2014 11:40 am

“The same growth mechanism of carbon dioxide content atmosphere occurred by the IPCC (1997 Report), between 120-130 thousand. years, which means that no it could cause a man and his civilization. It is therefore necessary to look for another explanation of the reasons temporary increase of atmospheric carbon dioxide, perhaps such as that proposed above. Climate change, changes in carbon dioxide emissions from the ocean are therefore a side effect of changes biological productivity of the ocean. It is controlled by cosmic processes already described by many researchers, including by Milutin Milankovitch. Warsaw, 25 October 2013, amended on February 6, 2014 year. ”
Bogdan Góralski

ren
December 31, 2014 12:40 pm

“Among the relatively large number of phytoplankton species occurs only a few in amounts that indicate their dominance across the whole Baltic Sea. Generally meet the spring diatoms Chaetoceros Achnanthes taeniata and wighamii and dinoflagellates Peridiniella catenata summer cyanobacteria Aphanizomenon flos-aquae and Nodularia spumigena along with various kryptofitami, and in the autumn diatoms Coscinodiscus granii and Thalassiosira baltica and Rhodomonas kryptofita minute. In winter abundance of algae is very low, and the propagation of very weak or non-existent. In the spring, when it is more more sunlight and the water warms up and is it enough In- żo of nutrients, diatom bloom starts and immediately after the dinoflagellates and various small flagellates. In summer, the phytoplankton is dominated by blue-green algae, and in the autumn diatoms again.”
http://ocean.ug.edu.pl/~oceju/CentrumGIS/dane/morze_baltyckie.pdf

Robber
December 31, 2014 2:56 pm

What appears to be pHraudulent is the term “ocean acidification”. It implies nasty acids are going to burn us when we go swimming. The oceans are alkaline (pH around 8) yet we going swimming in rivers and dams that may well be slightly acidic.
The largest variety of aquatic animals prefer a range of 6.5-8.0.
Of course Wikipedia has its usual CAGW/CC/CD correctness: “The pH of seawater plays an important role in the ocean’s carbon cycle, and there is evidence of ongoing ocean acidification caused by carbon dioxide emissions.”
Where is the peer reviewed literature that predicts that the oceans will reach a pH<7.0?

December 31, 2014 3:51 pm

Darn, I was slow to trademark Very Good Idea.
Best get working on Very Bad Thing, Very Good Thing, …
😉

December 31, 2014 3:58 pm

The Warmistas have no other interest in the pH of seawater, other than the to be able to predict the future ocean as a hot boiling acidic catastrophe maelstrom. CO2 present in sea water is 99% a bicarbonate, with barely 1% of it present as carbonic acid These strange people are only interested in fooling the population into believing their weird theory of CO2 being out of control.

Mark
December 31, 2014 4:05 pm

I keep hearing that glass based pH electrodes are too unreliable to measure pH to better than 0.1 pH units. That is completely incorrect, such inaccuracy is only seen in low conductivity solutions -which is NOT the case for seawater. My lab routinely measures pH to +/- 0.02 pH units with a combination electrodes and quality assurance is easy using calibrated buffer solutions (NIST traceable). The bad measurements seen in the raw data presented above are probably data entry errors and/or human error. Rejectin all ealy data is patentenly absurd.
HTH

Geoff Sherrington
Reply to  Mark
December 31, 2014 5:44 pm

Mark,
Have you systematically studied sea water that is in situ v. days to weeks after sampling? The effects of ussing containers of various compositions? Effects of filtered v. unfiltered? Filtered with fine v. coarse filters? Biologically active v. killed biota? Sampling the top mm, 5mm, 10 mm etc intervals? Noting high temperature gradients over such intervals, esp in still waters? Day v. night measurements? And the factorial combinations of all of the above?
Yes, you are claiming an accuracy for the glass electrode, but you cannot use that accuracy for past times when many of the above are known unknowns.
Sea water is moderately high in ionic strength and needs consideration of effects such as Debye and Huckel described. It commonly has suspended matter that can cause insidious instrumental drift. It commonly has biological activity that can do likewise.
The holistic accuracy is far worse than lab accuracy, rendering not only the glass electrode methods unreliable, but also other methods. If you have ever studied sampling theory for earth science systems, you will be aware that sampling the oceans as has been done, involves large errors irrespective of how pH is measured.
(I wrote a draft Masters’ thesis about relevant electrode complications).

ferdberple
Reply to  Geoff Sherrington
December 31, 2014 6:53 pm

same problem we face with glass thermometers. yet we don’t hear scientists crying out that we should scrap GISS and HADCRUT data in favor of the much more accurate RSS and UAH satellite data. scientific hypocrisy. cherry picking from start to finish.

Mark
Reply to  Geoff Sherrington
January 1, 2015 2:27 pm

None of the above affect the pH except ageing the sample, the glass electrode rejects all except protons which is why it works in the first place and is used to measure the pH of sewage ! Do your accept that a Nerstian slope is proof of the principle? A dye method is FAR less reliable in the presence of organics.
HTH

Mark
Reply to  Geoff Sherrington
January 1, 2015 2:46 pm

Hmm. I’m sure you could get a Masters from talking about lon known effects on glass pH electrodes. But, you chuck a bucket over the side of a ship, and dip a glass pH electrode in it and note the temperature. Simple