Guest Post by Willis Eschenbach
For a while now scientists have been raising the alarm about the effect of increasing atmospheric CO2 on the pH of the ocean. pH is a measure of whether something is acidic (pH below 7), alkaline, also called basic (pH above 7) or neutral (pH of 7). The ocean is slightly alkaline, and rainwater is slightly acidic. Here are some examples.
What’s happening is that the ocean is moving slightly toward neutral. However, “ocean neutralization” doesn’t sound alarming enough, so they’re falsely labeling it “ocean acidification”. Here are some quotes.
“Generally, shelled animals—including mussels, clams, urchins and starfish—are going to have trouble building their shells in more acidic water, just like the corals. Mussels and oysters are expected to grow less shell by 25 percent and 10 percent respectively by the end of the century… oyster larvae fail to even begin growing their shells.”
Ocean Acidification, Smithsonian Museum
“After exposing them to a range of acidity levels, UC Davis scientists found that under high CO₂, or more acidic, conditions, the foraminifera had trouble building their shells and making spines, an important feature of their shells. They also showed signs of physiological stress, reducing their metabolism and slowing their respiration to undetectable levels.”
Tiny Shells Indicate Big Changes to Global Carbon Cycle, UC Davis
“Like a piece of chalk dissolving in vinegar, marine life with hard shells is in danger of being dissolved by increasing acidity in the oceans. Ocean acidity is rising as sea water absorbs more carbon dioxide released into the atmosphere from power plants and automobiles. The higher acidity threatens marine life, including corals and shellfish, which may become extinct later this century from the chemical effects of carbon dioxide, even if the planet warms less than expected.”
Regardless of global warming, rising CO2 levels threaten marine life, University of Illinois
YIKES! EVERYONE PANIC!
I got to thinking about this, and I thought … wait a minute. There have been hard-shelled animals in the ocean since the end of the Cambrian Explosion about 485 million years ago. Say what?
Now, there’s a new study out in Science Magazine (paywalled, of course) that contains estimates of both atmospheric CO2 and oceanic pH since 485 million years ago. 485 million years ago is roughly the end of what’s called the “Cambrian Explosion Of Life”, a time when a huge number of life forms emerged on the earth.
Here’s their estimate of CO2 levels since the Cambrian Explosion.
Figure 1. Title says it all. I’ve added the modern increase at the recent end of the graph.
You might ask, “If the study is paywalled, how did you get the data”. Well, their Supplementary Online Information isn’t paywalled, and it contains this graphic.
Figure 2. Panel B, Figure S10, op. cit.
Note that the CO2 levels are shown on a log scale to visually minimize the size of the actual changes … but I digress. Sadly, they didn’t include a table of the data. So I had to digitize it. Takes a while, but I’m a patient man.
Figure 3. Digitization of the graph shown in Figure 2.
Looking back at Figure 1, the most remarkable features are the large and rapid drop in CO2 levels starting around 470 million years before the present (Ma BP), and the somewhat slower but almost as large rise starting around 430 Ma BP.
The 470 Ma BP drop is generally attributed to enhanced silicate weathering of the mountains by early land plants, and reduced volcanic CO₂ input. And the increase is generally attributed to reduced mountain weathering due to glaciation, along with an increase in volcanic CO₂ emission. Are those actually the causes? Unknown. The Late Ordovician glaciation only covered about 13%-14% of the land area, compared to about 25% of the land area during the most recent glaciation. So that part of the explanation seems unlikely, but what do I know?
In any case, the study also has a graph of the pH of the ocean over the same period of time. How accurate is it? Also unknown. Presumably, however, it’s currently our best estimate of the variations of oceanic pH over 485 million years. Again I digitized the data. Here’s that graph.
Figure 4. Again, title says it all.
Now, there are several noteworthy points in this graph. First, at no time in the past 485 million years has the ocean been acidic. It has always been alkaline (basic), with a pH always greater than 7 (neutral pH).
Second, over that entire time, there has been a huge variety and profusion of shelled animals living in the ocean, apparently unbothered by the variations in alkalinity.
Third, in the upper right of Figure 4 is a tiny vertical line with horizontal “whiskers” at the top and bottom. It shows the modern change in pH since 1850, the change that has all the megabrains calling the Climate 911 hotline to report an emergency … color me unimpressed. We’ve run the oceanic pH experiment over the last half billion years. Shelled creatures didn’t disappear.
TL;DR version? Life has flourished, both above and below the surface of the sea, through periods when atmospheric CO2 has varied up to almost ten times the current level. As a result, the myriad of alarmist claims that increasing CO2 is some kind of death sentence for life either on the land or in the ocean all run aground on a reef of hard facts.
Don’t believe me about pH and creatures with shells? Ask the chambered nautilus, a lovely cephalopod with a hard shell. I once saw a school of them while scuba diving, and I have the shell of one that I picked up years ago on a beach on one of the outer islands in Fiji.
It’s one of the most ancient creatures in the sea, and it has existed in a virtually unchanged form for half a billion years … funny how the changes in oceanic pH didn’t disturb it one bit.
Best to all on a sunny afternoon,
w.
Yeah, you’ve heard it before … when you comment, please quote the exact words you are discussing. I can defend my words; I choose them carefully. I cannot defend your understanding of my words.
My Other Analyses Of the Ocean Neutralization Question:
pH Sampling Density 2014-12-30
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I love the coral reefs of the planet. In my childhood on a dusty cattle ranch in the Western US, I decorated my mental imaginarium of the world with images of unbelievably colored reefs below white sand beaches, with impossibly shaped fish and strange, brilliant plants. But when I finally…
The Electric Oceanic Acid Test 2010-06-19
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A Neutral View of Oceanic pH 2015-01-02
Following up on my previous investigations into the oceanic pH dataset, I’ve taken a deeper look at what the 2.5 million pH data points from the oceanographic data can tell us. Let me start with an overview of oceanic pH (the measure of alkalinity/acidity, with neutral being a pH of…
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The Ocean Is Not Getting Acidified 2011-12-27
There’s an interesting study out on the natural pH changes in the ocean. I discussed some of these pH changes a year ago in my post “The Electric Oceanic Acid Test“. Before getting to the new study, let me say a couple of things about pH. The pH scale measures…
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The British tabloid “The Guardian” has a new scare story about what is wrongly called “ocean acidification”. It opens as follows: Sounds like the end of times, right? So let me start with a simple fact. The ocean is NOT acidic. Nor will it ever become acidic, except in a few isolated locations. It i…
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“My Other Analyses Of the Ocean Neutralization Question:”
The excuse is that all researchers actually understand that it is not really an acid pH, therefore not relevant. If you want to get really complex check out estuaries. Among other earlier examples before the ‘renaming.’
Park, K, D. W. Hood and H. T. Odum. 1958. Diurnal pH variation in Texas bays and its application to primary production estimation. Publications Institute Marine Science. Univ. Tex. 5:47-64. pH varied from just below 8.0 to just above 8.6, but sometimes not below 8.2 or 8.5. Conclusion was that “…indirect evidence indicates that calcium carbonate precipitation and solution do not follow inorganic solubility relationships. Blue crabs know this.
So much literature, even on estuaries, but to be sure earlier studies for whatever reasons may be relevant. Seems to be a failing about needing too much homework. Now asking different questions, chemical competence (know about pK and pOH) or just boilerplate, cut and paste?
Willis,
It is not correct to generalize that “What’s happening is that the ocean is moving slightly toward neutral”. The measurement uncertainty is too great. So, I take it that you are quoting others. You have referenced several articles of your own relating to uncertainty. Here are some more factors.
“Environmental” chemists often use the wrong definition of pH. They use “the negative logarithm of the hydrogen ion concentration” when “concentration” should be “activity”. These 2 terms are related in complicated ways, see the Debye–Hückel equations. The difference matters when there are high concentrations of other dissolved species such as the sodium chloride in ocean waters.
A lot of past measurements were done with pH electrodes (on which I wrote a draft Master’s thesis). With careful use, one can see that natural waters as sampled can give a different pH after they are filtered. The pH in the presence of suspended solids (like seaweed and zooplankton) can slowly drift over time, so filtration is often preferred. Even in controlled lab conditions, it is hard to maintain and reproduce pH values in synthetic mimics of natural waters to +/- 0.1 pH units.
The concept of buffering of pH is ever-present for ocean waters. Some authors discuss it, others ignore it. Buffering reacts to minimise change.
But in the end, despite various discussions about uncertainty, researchers tend to parrot the Establishment line as if there is little uncertainty. Maybe their income depends on it.
Because the uncertainty is so large, I cannot agree with this Establishment line that ocean pH has changed from 8.2 to 8.1. Example: “Prior to the Industrial Revolution of the 18th to 19th centuries, the ocean’s average pH was about 8.2. Today, the ocean’s average pH is 8.1. This means that the ocean today is about 30 per cent more acidic than in pre-industrial times. By 2100, the pH of the ocean could decrease to about 7.8, making the ocean 150 percent more acidic and affecting half of all marine life, according to the Intergovernmental Panel on Climate Change (IPCC) Sixth Assessment Report.”
Geoff S
Fascinating, Geoff. The ALPHA station near Hawaii shows decreasing pH. My research finds the following. Your comments are gratefully invited.
w.
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Procedures for Calculating the pH of Seawater at the ALPHA Station
Sampling and Measurement Overview
At the ALPHA (ALOHA) station, seawater pH is determined using a precise and standardized spectrophotometric method, primarily following the protocol established by Clayton and Byrne (1993)12. This method is widely recognized for its accuracy in oceanographic research.
Step-by-Step Procedures
Summary Table: Key Elements of the pH Measurement Protocol at ALPHA Station
StepMethod/InstrumentScale/StandardizationNotesSample CollectionCTD-rosetteN/AKnown depths, minimizes contaminationMeasurementSpectrophotometry (m-cresol purple)Total Scale @ur momisugly 25°CHigh precision, standardized methodCalibrationTotal Scale, no +0.0047 correctionConsistent with protocolsOlder data converted for consistencyQuality ControlDuplicate samples, CV calculation<0.02% CV typicalRigorous data validation
References for Further Detail
This approach ensures that pH data from the ALPHA station are accurate, precise, and comparable across time and with other oceanographic datasets.
More below.
The stated uncertainty of the pH measurements at the ALPHA (ALOHA) station is expressed as the pooled annual coefficient of variation (CV) of the pH analysis. For the year 2022, this value was 0.018%. This CV was calculated by averaging the mean CV of duplicate samples collected on each cruise, reflecting the high precision and reproducibility of the spectrophotometric pH measurement method used at the station1.
More below
Seawater used for the core time-series pH measurements at the ALPHA (ALOHA) station is not filtered prior to analysis. This practice aligns with standard oceanographic protocols for long-term monitoring programs like the Hawaii Ocean Time-series (HOT), which aim to capture the natural state of the seawater as it exists in situ, including all dissolved and particulate components1. Filtration is generally avoided for these core measurements because:
In summary, filtration is not performed for core pH time-series measurements at the ALPHA station to ensure that the data accurately reflect the natural seawater conditions and remain consistent with international ocean monitoring standards1.
Willis,
My apologies if I caused you to spend time gathering those many references from Hawaii, most of them familiar. I do not disagree with what you wrote. I was adding to your experiences with educational pH lab work, with my experiences of years at the commercial lab bench to service clients who were tough customers controlling my income. I departed that scene when I could not perform as well as competitor labs that invented some of their estimates of prowess.
Part of the game involves rejection of outlier measurements. The Hawaii people do it, seen in your references, “Results are rigorously quality-controlled, and any data with questionable calibration or measurement issues are flagged and excluded from main datasets1.” It is also done for CO2 in air at Mauna Loa, for estimates of Total Solar Irradiation from satellite measurements, for early studies of Argo buoys with JPL oceanographer Josh Willis rejecting some, many early measurements of CO2 in air rejected and of course many daily temperature measurements “adjusted” to conform. Climate research provides many examples of data uncertainty related to rejection. It opens the door to those who might adjust to suit a mission. The links I just gave illustrate the concern that this is causing.
I do not disagree that there is evidence of some fall in ocean pH over the last 30 years, in certain places (that might be most places) and times and depths and seasons and many other variables that we can imagine but that are not well quantified. Hawaii results are but a tiny part. The oceans are huge, as you would have found by flying from US to Australia (as I have done many times). I agree with their tight scientific approach and hope that tight scientific control is used elsewhere – but it was not so much used in the past. My article was more about the pH meter era and its large uncertainty.
Here is a graph of alleged ocean pH changes from your Hawaii references, to introduce a new science talking point. Mostly, people work with the Y-axis. Here, the X-axis is time, that seems to be the time of sampling the ocean, but is it valid choice? The ocean is forever changing. How can we tell if the data is reflecting an event that happened at another time? A large eruption (not unknown on Hawaii) might have caused a pH seen at time of sampling but caused by events some years prior. So, even the X-axis has uncertainty.
The matter of chemical buffering was raised in many WUWT comments. Not many people have been trained in enough chemistry to understand it. The uncertainty of ocean pH changes is not settled until buffering is quantified and accepted.
In short, I am not claiming that there is no change to ocean pH. I am claiming that the uncertainty is much higher than some prominent researchers find acceptable, so they ignore it and stick to unreal Establishment dogma.
p.s. At age 8, in 1949, my brothers and I spent a summer fortnight on a raw tropical island on the inner Great Barrier Reef. Rare foreign shell collectors, museum people they said, paid us a small fortune to find lovely specimens of live Nautilus, beautiful creatures that were selected to illustrate your article. But we stopped after a couple of sales because it was not right.
Geoff S
Geoff, thanks for the clarification and further information. I don’t disagree with most things you’ve said, and your links to your previous posts (only some of which I’ve read) are particularly interesting.
Best regards,
w.
Willis, it seems to me there is already a huge natural ‘experiment’ showing that ocean life can easily adapt to many of these changes others are declaring catastrophic. The Amazon reef system discovered just a few tears ago.
I cannot find the smoking gun of proof, but here’s a short version of the evidence:
There is a massive reef system in the Atlantic at the mouth of the Amazon River.
The system is home to many species of coral, fish, and shellfish, all thriving on the nutrients brought by the river. The river deposits are sometimes thick enough to muddy the waters of the reef system.
The waters of the Amazon River are quite warm, very low salinity, and actually ACIDIC, not simply less alkaline.
What I can’t find are actual temperature, pH, and salinity data of the reef system, itself, (and obviously nothing about how variable those conditions are).
If you ever see that type info I would be very interested in reading about it and the implications they have on the research to date.
Sounds like BS to me.
As the oceans warm, they outgas CO2, so in that case the oceans should be becoming more alkaline
It is not a one variable process.
Certainly your point has merit in that it affects to aggregate results, but by itself, exclusive of everything else, it explains not much at all.
Do not fall in with the “CO2 is the control knob” crowd.
Story tip
https://www.wsj.com/business/logistics/car-carrier-sinks-in-pacific-after-blaze-on-deck-carrying-evs-25fefe77
44% of the weight of coral and shell is carbon dioxide. The rest is cement.
Cement? Pardon me, I know what you mean, however, it is well known that China is making man made islands, purportedly for military purposes, by pouring cement and other materials on coral reefs.
The formation of limestone inorganically is very informative. If you heat limestone you get quick lime and carbon dioxide. Quick lime is the basis of cement. It you mix quick lime with water it releases heat and hardens in minutes to hours. However this is not the whole story. Over days to weeks the hardened cement absorbs carbon dioxide while releasing all the absorbed water. This strengthens the cement. In the end no water is consumed. It is fully recycled and the end product is limestone. A mix of quick lime and carbon dioxide. Water serves as a catalyst. Please explain how adding carbon dioxide would inhibit this reaction.
It could be argued that concrete is somewhat carbon neutral. The CO2 driven off to produce quick lime from limestone equals the CO2 absorbed by concrete during the strengthening process.
No graph with the co2 and pH together?
They’re sampled at different times. I could interpolate both ways. Thought about it, then decided that was enough for one post. Hang on … we know pH is proportional in some sense to the log of the CO2. Give me a minute … well, of course it takes more than a minute but most interesting.
Looks like that will be the subject of my next post. Stay tuned.
w.
if you give me an email Willis, I can send you a PDF of the study. Kevin Roche