Guest Essay by Kip Hansen
Preview: In this essay I will discuss the efforts of various scientific bodies and individual scientists to regularize, to bring into line with correct scientific procedures, the budding field of science investigating the effects of increasing atmospheric concentrations of CO2 on the oceans, its chemical make-up including pH, the atmosphere/ocean carbon cycle and what those changes might mean for ocean organisms over the next 100 years – a subject popularly known as Ocean Acidification (hereafter OA).
The 6 August 2015 issue of the journal Nature carried a highlight article under the subject heading Ocean Acidification entitled “Seawater studies come up short — Experiments fail to predict size of acidification’s impact.” (.pdf here)
The Nature highlight article, by Daniel Cressey (a full time Nature reporter based in London) states:
“The United Nations has warned that ocean acidification could cost the global economy US$1 trillion per year by the end of the century, owing to losses in industries such as fisheries and tourism. Oyster fisheries in the United States are estimated to have already lost millions of dollars as a result of poor harvests, which can be partly blamed on ocean acidification.
The past decade has seen accelerated attempts to predict what these changes in pH will mean for the oceans’ denizens — in particular, through experiments that place organisms in water tanks that mimic future ocean-chemistry scenarios.
Yet according to a survey published last month by marine scientist Christopher Cornwall, who studies ocean acidification at the University of Western Australia in Crawley, and ecologist Catriona Hurd of the University of Tasmania in Hobart, Australia, most reports of such laboratory experiments either used inappropriate methods or did not report their methods properly.”
(all in reference to Cornwall and Hurd ICES J. Mar. Sci. http://dx.doi.org/10.1093/icesjms/fsv118 ; 2015 )
followed by:
“Cornwall says that the “overwhelming evidence” from such studies of the negative effects of ocean acidification still stands. For example, more-acidic waters slow the growth and worsen the health of many species that build structures such as shells from calcium carbonate. But the pair’s discovery that many of the experiments are problematic makes it difficult to assess accurately the magnitude of effects of ocean acidification, and to combine results from individual experiments to build overall predictions for how the ecosystem as a whole will behave, he says.”
(Just to be clear, the two quotes above are from the Creesey Nature highlight.)
The paper by Cornwall and Hurd is a masterful piece of science of a type rarely seen in academia today (with a few exceptions to be discussed later). It investigated the experimental design of the current crop of papers in a scientific field and evaluated whether or not the study designs and results analyses used were appropriate to return scientifically meaningful results.
This paper was published in International Council for the Exploration of the Sea (ICES) – Journal of Marine Science. Here’s the abstract:
“Ocean acidification has been identified as a risk to marine ecosystems, and substantial scientific effort has been expended on investigating its effects, mostly in laboratory manipulation experiments. However, performing these manipulations correctly can be logistically difficult, and correctly designing experiments is complex, in part because of the rigorous requirements for manipulating and monitoring seawater carbonate chemistry.
To assess the use of appropriate experimental design in ocean acidification research, 465 studies published between 1993 and 2014 were surveyed, focusing on the methods used to replicate experimental units. The proportion of studies that had interdependent or non-randomly interspersed treatment replicates, or did not report sufficient methodological details was 95%. Furthermore, 21% of studies did not provide any details of experimental design, 17% of studies otherwise segregated all the replicates for one treatment in one space, 15% of studies replicated CO2 treatments in a way that made replicates more interdependent within treatments than between treatments, and 13% of studies did not report if replicates of all treatments were randomly interspersed. As a consequence, the number of experimental units used per treatment in studies was low (mean = 2.0).
In a comparable analysis, there was a singnificant decrease in the number of published studies that employed inappropriate chemical methods of manipulating seawater (i.e. acid–base only additions) from 21 to 3%, following the release of the “Guide to best practices for ocean acidification research and data reporting” in 2010; however, no such increase in the use of appropriate replication and experimental design was observed after 2010.
We provide guidelines on how to design ocean acidification laboratory experiments that incorporate the rigorous requirements for monitoring and measuring carbonate chemistry with a level of replication that increases the chances of accurate detection of biological responses to ocean acidification. “
(I have added paragraphing to the above for readability – kh)
Note: Despite heroic efforts, I have been unable to find a freely available full copy of C&H 2015 online. Chris Cornwall kindly supplied me with an Advance Access .pdf copy of the full study and the supplemental information file. Those wishing to read the full study should either email Dr. Cornwall requesting a copy or email me (my first name at the domain i4 dot net).
First, let me point out that Chris Cornwall and Catriona Hurd are OA research insiders. Unfortunately, the title of the Nature highlight makes their study sound like an indictment of OA research, which it is not.
Chris Cornwall tells me (in personal communication) that their study has been generally well received in the OA field and that “Many scientists have received the suggested solutions with open arms.” And while the Nature highlight will go a long ways towards making the points raised in C&H 2015 clear to scientists all across the OA research field — a good thing — he felt that the Nature piece had elements that were “overly dramatic or incorrect” which had been latched onto by the popular press. Further, Chris says “Debates between scientists about improving a field of research do not invalidate that field, contrary to that reported by the Daily Mail.”
(Late addition: Chris Cornwall responds to the Daily Mail here. There is some slight contradiction between his public statement and his published paper but he does have to continue to work in the field – Cornwall and Hurd intentionally did not publish the details of their analyses of the 465 papers – which ones were appropriate and which inappropriate and why – they only published, as a supplement, a list of the titles of those studies surveyed, for what I assume is the same reason.)
Just what have he and Catriona Hurd done? They have looked at published OA papers from 1993 to 2014 – 465 of them, which must have been an incredibly time consuming task — mostly laboratory manipulation experiments (manipulating atmospheric CO2 concentrations associated with ocean water tanks, usually with oceanic organisms, and pH manipulation of the same). They evaluated each one for inappropriate experimental design and/or analysis of results. The main issue and the major problem with the papers, though not the only one, dealt with the replication, or lack of, of experimental units.
Definition: Experimental units for this discussion can be thought of as individual tanks of sea water + organisms to be studied + treatment (or lack of treatment, in the case of a control tank). In the following diagram, from Cornwall and Hurd (C&H 2015), only experimental designs precede by the letter A are acceptable – all those preceded by B are not. (ref: Hurlbert 1984). (In 2013, Hurlbert used the definition “the smallest… unit of experimental material to which a single treatment (or treatment combination) is assigned by the experimenter and is dealt with independently …”).
The point being that “Regardless of the degree of precision that the treatment is applied and its effects measured, if treatment effects are confused with the effects of other factors not under investigation, then an accurate assessment of the effects of the treatment cannot be made.” If experimental units are not independent, if they are not truly randomized, if co-confounders can be seen to exist, then the results are not scientifically reliable.
What did C&H find in this regard? Out of the 465 OA studies done between 1993 and 2014, “The proportion of studies that had interdependent or non-randomly interspersed treatment replicates, or did not report sufficient methodological details, was 95%.” That leaves just 5% of the studies judged to have appropriate experimental designs.
We all know that there are many things that can go wrong in lab experiments such as these, those which take months and months, require constant monitoring of finicky details and that can be sabotaged by a moment’s inattention of a lab assistant. These factors we understand and are part of the difficulty of all lab work. But when the original experimental design is insufficient for the purpose from the outset then time, money, and effort are wasted and results become difficult or impossible to interpret – certainly impossible or very difficult to use to perform any sort of meta-analysis across studies.
Further, “the number of experimental units used per treatment in studies was low (mean = 2.0).” Think about that — imagine doing a medical study, an RCT, but using only 2 patients per cohort. Then consider that there are obvious co-confounders with the two patients, such as being siblings! No journal would touch the resultant paper – it would have no significance at all. Granted, one might get away with reporting it as a Case Study, but it would never be considered clinically important or predictive. And yet that is precisely the situation we find generally in OA research – very small numbers of experimental units poorly isolated, often with co-confounders that obfuscate or invalidate treatment effects.
C&H report (at the head of the discussion section):
“This analysis identified that the most laboratory manipulation experiments in ocean acidification research used either an inappropriate experimental design and/or data analysis, or did not report these details effectively. Many studies did not report important methods, such as how treatments were created and the number of replicates of each treatment. The tendency for the use of inappropriate experimental design also undermines our confidence in accurately predicting the effects of ocean acidification on the biological responses of marine organisms.”
The authors maintain nonetheless that even poorly designed studies contain useful information, even if getting at it requires a full re-analysis of reported results. Some experiments however are hopelessly compromised by poor study design.
Having determined the biggest problem to be:
“Confusion regarding what constitutes an experimental unit is evident in ocean acidification research. This is demonstrated by a large proportion of studies that either treated the responses of individuals …. to treatments as experimental units, when multiple individuals were in each tank, or used tank designs where all experimental tanks of one treatment are more interconnected to each other than experimental tanks of other treatments (181 studies total).”
C&H proceed to give suggestions on proper experimental design that will prevent the problems found in the majority of previous studies as well as a series of suggestions regarding statistical evaluation of results. They attempt to set a gold standard for OA research in which known problems are avoided to improve reliability, significance, and usefulness of results.
C&H recommend 1) various approaches to be determined and adopted before the OA manipulation system is designed, 2) lab layout and randomization of the positions of experimental tanks, 3) measurement schemes to avoid pseudo-replication and statistical confusion caused by treatment of measurements — either interdependent measurements treated as independent, or multiple measurements of the same unit treated as independent measurements, and other similar offenses, 4) tips for reviewers (and self-review by authors) . Those interested in the details of this should read this section of the study – it is a valuable lesson in how complicated good experimental design can be even for “simple” hypotheses (I give suggestions above on how to obtain a full copy of C&H 2015).
This study follows up on a major effort in 2010 along the same lines – an effort by the European Project on OCean Acidification (EPOCA) – which produced the booklet “Guide to best practices for ocean acidification research and data reporting” (mentioned in C&H 2015), which gave strict guidelines meant to correct the 21% of pH perturbation experiments that, as of 2010, had been found using methods that did not properly replicate real ocean carbonate chemistry (see sections on seawater carbonate chemistry). The good news from C&H 2015 is that the percentage of studies that contained gross carbonate chemistry errors in the OA studies after 2010 were reduced to just 3% (down from 21% before 2010). The rest of C&H 2015 is the bad news: even though the “Guide to best practices…..” contained an entire section on “Designing ocean acidification experiments to maximise inference” (Section 4 of the guide), 95% of studies surveyed in 2014 failed to meet minimal standards of experimental design (some of these, of course, must have been carried out before the guide was published – nonetheless, C&H report no improvement in experimental design between 2010-2014).
This new field is to be congratulated on its internal attempts to set itself right – to correct endemic errors in its research and educate those involved in better ways to conduct that research so that results will be significant and meaningful in the real world – results that not only are correct and get published, but that add to the sum total of human knowledge.
And yes, it is a shame that so much effort and so many research dollars have been spent for results that, so far, cannot tell us very much that is reliably useful and almost nothing that can be considered accurately predictive. But the hopeful thing is that this field of endeavor is actively engaged in self-correction.
Try to imagine such a thing happening in some other field of Climate Science – insider scientists producing a survey of research that points out that the majority of those studies about some aspect of Climate Science are seriously flawed and will have to be redone with experimental designs and statistical approaches that will actually produce dependable, scientific results.
Back in the OA world, Chris Cornwall has expressed his hope that their new paper in ICES – Journal of Marine Science (and the Nature editorial highlight which significantly raised its profile), will bring improvements to OA experimental design over the next five years similar to those improvements they found for the chemistry aspects of OA studies post-2010.
I hope so too – Chris Cornwall and Catriona Hurd have my congratulations and I wish the entire OA field success, looking forward to new research based on proper experimental design and correct oceanic carbonate chemistry.
* * * *
And elsewhere in Science?
Psychology has been rocked by this NY Times story – “Many Social Science Findings Not as Strong as Claimed” which reports about the Reproducibility Project: Psychology. The original report summary is here: Estimating the Reproducibility of Psychological Science. The Times quotes Ioannidis (author of “Why Most Published Research Findings Are False”):
“Less than half [of 100 experiments were able to be replicated]— even lower than I thought,” said Dr. John Ioannidis, a director of Stanford University’s Meta-Research Innovation Center, who once estimated that about half of published results across medicine were inflated or wrong. Dr. Ioannidis said the problem was hardly confined to psychology and could be worse in other fields, including cell biology, economics, neuroscience, clinical medicine, and animal research.”
The Reproducibility Project (RP) was attempting to validate studies, not invalidate them. They involved original authors in the design of replication attempts. Psychology has long known that many of their journal articles reported experiments that were unlikely to be correct, which exaggerated effect size and significance or did not report real effects at all. The RP is trying to help Psychology as a field of research to regain some semblance of reliability and public confidence, especially after a series of high profile exposés of falsified data and subsequent retractions.
Ioannidis gives a series of suggestions in his “Why Most Published….” paper on what could be done to improve this dismal record.
Reading Ioannidis will give you a lot of insight into what is wrong with CliSci research. Among the suggestions: “large studies with minimal bias should be performed on research findings that are considered relatively established, to see how often they are indeed confirmed. I suspect several established “classics” will fail the test.” For examples of this, see “Contradicted and initially stronger effects in highly cited clinical research” and, from the Mayo Clinic, “A Decade of Reversal: An Analysis of 146 Contradicted Medical Practices” .
Annemarie Zand Scholten & her team at the University of Amsterdam have produced an online course at https://www.coursera.org called Solid Science: Research Methods primarily aimed at social science students/researchers on the theory and practice of proper experimental design.
In the field of forecasting, J. Scott Armstrong has been leading the way with “Standards and Practices for Forecasting.”. There are several leaders in Statistics as well, battling against the dreaded “P-value hacking” (and here).
Those of us (if there is an “us” amongst readers) who believe we need better (not just more) and Feymanian-honest (not just correct) science should applaud these efforts to improve various fields of research, to point out their flaws while avoiding the temptation to “throw the baby out with the bathwater”.
A lot of the ongoing conversation regarding what to do about the what-some-believe-to-be-broken peer-review system include such things as advanced registration of all proposed experiments with their hypotheses, approvals, proposed methods and metrics. Along with this, repositories for all research data and results, raw and processed, all findings, along with resultant papers and subsequent corrections. I believe all these efforts should be supported as well.
I encourage readers to share, in comments, other “self-correction of science” efforts that they are aware of.
It is long past time to end Climate Science’s standard approach which seems to be “Instead of Correction, Collusion.”
(and “Yes, you may quote me on that.”)
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Author’s Comment Policy: I am happy to try to answer your questions about the topics I have brought up in this essay. I act here as a free-lance science journalist, and not a climate or oceanic scientist. Though somewhat knowledgeable, I am unable, and mostly unqualified, to answer questions regarding the science of AGW, CAGW, Global Warming, Global Cooling, Climate Change, Sunspot numbers, solar irradiation, ocean/CO2/carbonate chemistry or other related topics – and will not engage in conversations on those issues. It would be nice if comments here could be about the positive side of self-correcting science efforts and not on the “I knew those blank-ity-blank ocean acidification guys were full of it” side. Thank you for reading.
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You guys are way overthinking this…
Just tell us when the oceans will run out of buffer.
Reply to Latitude ==> If only it were that easy.
CO2 + H2O +NaCl = propaganda to throw at the masses. Given how much the UN holds humanity, the great unwashed, in disdain, why do they even bother?
Isn’t it refreshing to find folks trying to improve rather than manipulate science.
Except it isn’t science, but pseudo-science.
Reply to jake ==> It is refreshing to find someone who apparently read my essay and understood what it was about.
“Ocean Acidification: Trying to Get the Science Right”. The first two words take you outside the realm of science.
The whole climate science methodology is flawed. Come up with a theory then look for data that support your theory. Ignore or change data that do not support your theory.
Yeah, why not call it “Ocean ph Fluctuations” – maybe “O phlucks” for short.
/grin
Kip Hansen –
It’s good to see Science’s self-correction process in action.
You may have information (or links) I’ve been looking for on a relevant issue (I’ve only skimmed the EPOCA link):
> Many limestone-using marine organisms exist in an environment of that limestone (phytoplankton in a suspension of their skeleta, shellfish adjacent to accumulations of their shells, etc). If this isn’t controlled for, I don’t think you can generalise from tank to ocean. If an organism pioneering outside its normal environment is disadvantaged, inappropriate experimental design may confound this with a p(CO2) effect.
> Crystallisation/dissolution is a surface phenomenon. Suitable materials (some available to marine life) can temporarily transform mineral surface properties. Marine life long ago learned to exploit the bicarbonate – limestone chemistry; has it also learned to manipulate limestone surfaces? I offer the falsifiable hypothesis: “Live” limestone is less affected by a p(CO2) change than “dead” limestone from the same source in the same environment.
I (like you) don’t minimise the experimental difficulties in getting robust and relevant results here.
Reply to Peter Shaw ==> The EPOCA booklet, starting at page 20, gives a very good rundown of basic ocean carbonate chemistry and further on makes recommendations on experimental perturbation techniques that will at last nominally mimic real ocean chemistry.
Ferdinand Engelbeen September 5, 2015 at 12:46 am
“As a lot of sea life is in the mixed layer, it is important to know what the influence of a CO2 doubling is. Until now there is no measurable influence on any sea life, thus we need good designed experiments to know what may happen with elevated CO2…”
I’m less of a “certaintist” and would phrase that as:
“As a lot of sea life is in the mixed layer, it may be important to know what the influence, if any, of an atmospheric gradual increase to a CO2 doubling is. Until now there is no measurable influence on any sea life, thus we need good designed experiments to know what may happen, if anything, with gradually increasing elevated atmospheric CO2 levels.”
Since we’ve seen “no measurable influence” perhaps that is because there is no measurable influence?
Agreed…
To know it for sure, we need experiments, which anyway should be shorter than 85 years, thus not the same as what happens in real oceans…
Acidification, shmashmidification.
Has any comparable research been conducted on “Ice cores, getting the science right” or “Tree rings, getting the science right” or “Polar bears, getting the science right” or “Ice sheets and glaciers, getting the science right” or “Science, getting the science right”?
Nicholas –
I believe the answer is “yes”, it has, but only by the people who actually want to get it right.
(For Polar Bears, for example, see http://polarbearscience.com/ )
The people who don’t want it to be gotten right aren’t telling us about that, though.
Reply to Nicholas Schroeder ==> Good question!
As JohnWho points out, Susan Crockford has been working on polar bear science, but not in a formalized sense.
There have been suggestion for a Red Team, Blue Team approach.
John Ioannidis has publicly suggested retesting major “givens” in various fields believing that if carefully retested, many of them will fail.
Science definitely needs such efforts and professional and academic organizations should establish bodies, anonymous if necessary, to carry out such studies and publish booklets like the EPOCA guide.
Nicholas,
In the case of ice cores, indeed that happened. After lots of pitfalls in the early days (contamination, cracks, storage conditions,…), Etheridge e.a. tried to answer these pitfalls. That resulted in three drillings at Law Dome, with different drilling techniques (wet and dry), measuring CO2 top down from atmosphere to bubble closing depth, etc. The results can be found in his 1996 work:
“Natural and anthropogenic changes in atmospheric CO2 over the last 1000 years from air in Antarctic ice and firn.” Journal of Geophysical Research 101:4115-4128.
http://onlinelibrary.wiley.com/doi/10.1029/95JD03410/abstract
For $6 you may read the full article…
CO2 measurements in air were quite chaotic in the days before Mauna Loa. One man, C.D. Keeling offered new insights and methods for where to measure and with much better instruments than in the early days, including rigorous calibration procedures to maintain the best available “background” data.
One can only hope that one day somebody stands up to do the same with the ground station temperature measurements…
Several months ago we discussed an effort to get to the bottom of the justification, or lack thereof, for the many adjustments and other manipulations of the surface temperature data.
Presumably this effort is ongoing.
That statement brought to mind the monkeys that were asphyxiated with pot smoke to prove it caused brain damage in the 70’s under Nixon.
Amazing what ideological agendas can get away with and call “science”.
Most of the CO2 “dissolved” in the oceans does not dissociate into the ocean Carbon positive and negative ionic species, it remains molecular CO2. CO2 loves to swim.
www2.hawaii.edu/~kinzie/…/470/CO2solubility.doc
“(2) CO2 (l) + H2O (l) H2CO3 (l)
This reaction is kinetically slow. At equilibrium, only a small fraction (ca. 0.2 – 1%) of the dissolved CO2 is actually converted to H2CO3. Most of the CO2 remains as solvated molecular CO2. As equation:
In fact, the pKa most reported for carbonic acid (pKa1 = 6.37) is not really the true pKa of carbonic acid. Rather, it is the pKa of the equilibrium mixture of CO2 (l) and carbonic acid. Carbonic acid is actually a much stronger acid than this, with a true pKa1 value of 3.58.”
That 99% of “dissolved” CO2 remains solvated CO2 molecules is completely ignored by hundreds of ocean chemistry images one can google. They all show immediate dissociation of all CO2 to carbonic acid.
+1
Thanks kindly, even if I don’t learn anything else today, this will still be a day of mental growth for this old guy.
gymnosperm,
You are grossly misinformed. Typical mid-ocean surface seawater composition is
undissociated CO2 9.9 micromolal
carbonate ions 232 micromolal
dissolved inorganic carbon 1980 micomolal
Dissolved inorganic carbon is the sum of CO2, bicarbonate, and carbonate. So undissociated CO2 molecules are 0.5% of the total.
The composition is from measurements made at Station Aloha as part of the Hawaii Ocean Time-series: http://hahana.soest.hawaii.edu/hot/products/products.html
Hmmm. So either my source is wrong, or it is for distilled water and not seawater and there is a huge difference. Does one expect radically more dissociation in a negative ionic soup? Decreased fugacity?
Another possibility is that the photosynthetic plankton are depleting ocean surface water of molecular.
gymnosperm,
“it is for distilled water and not seawater and there is a huge difference.”
Yep. The key issue is pH, since CO2 (or, if you prefer, carbonic acid) is an acid. Seawater has pH near 8, rainwater is near pH 5. So the ratio of bicarbonate to CO2 is about 1000 times as large in seawater as in near pure water.
“Does one expect radically more dissociation in a negative ionic soup?”
The positive and negative ions also have an effect since the ionic charges increase the dissociation of acids. So the pKa gets smaller (bigger Ka) and weak acids are stronger in an ionic solution than in pure water. But that is only something like a factor of 3.
Mike M.,
Describing the pH of seawater doesn’t really get at the reason dissociation should be so strikingly different. The difference appears to be 99% in seawater. Why?
gymnosperm,
“The difference appears to be 99% in seawater. Why?”
pH. Or, if you prefer, the presence of a base, CaCO3, leading to the reaction
CO2 + H2O + CO3= -> 2HCO3-
Really just two different ways of saying the same thing.
Mike,
Wow, my comment got translated a bit.It was written less than one percent dissociated in distilled water and more than 99 per cent in seawater (avoiding special characters).
CO2 + H2O + CO3= -> 2HCO3-
The same reactions occur in distilled water.
Reply to gymnosperm ==> Read the EPOCA guide starting on page 20 for a very detailed explanation of ocean carbonate chemistry.
Doesn’t really address the dissociation issue. On another note, when the second sentence of the EPOCA preface reads, ” The ocean presently takes up one fourth of the carbon CO2 emitted to the atmosphere from human activities.”, and this bold statement implying net ocean uptake of 2.5 GtC annually doubles the net uptake in the most modern Carbon cycle models, a good place to start improving the science would be right here. What is the basis for this? I’d personally love it because it would make it much easier to balance my isotope integrated Carbon cycle.
Reply to gymnosperm ==> As in many fields, it is important to separate the politically motivated introductions and executive summaries from the work of actual scientists in the science sections.
Perhaps someone can explain to me why the oceans will absorb an appreciable amount of CO2 if the ocean temperatures increase per the GW theory (i.e., increase in atmospheric CO2). With an increasing temperature, the oceans will release CO2. I get it that the CO2 in the ocean and atmosphere reach an equilibrium, but won’t the increase in ocean temperatures and correspondingly release of CO2 not offset the effect from increased CO2 composition in the atmosphere and maintain a relatively constant ocean CO2 composition?
Reply to Rich ==> In a word, “No”, with the addition of, “If it were only that easy”.
Rich ==> I’m in no way an expert, but my GUESS is that at lower levels of atmospheric CO2, the correlation between changes in CO2 concentration in air and water is more or less linear. With a slight decrease in solubility if temperatures increase. I think that’s what Henry’s Law says.
However, at some point, the solution will become saturated with CO2 (I have no idea hom many ppm of atmospheric CO2 that is — a great many I should think). Above saturation, more atmospheric CO2 is presumably going to have little effect on acidity and the temperature dependence of dissolved CO2 concentration is possibly going to come into play and drive acidity down as additional CO2 increases temperatures … maybe …
So what is being studied, the natural 96%, or man’s 4% or a combination?
I understand coastal ph levels can fluctuate over a wide range during the day and there seems to be no effect on the fishies or shell bearing.
Reply to nc ==> It doesn’t really matter where the atmospheric CO2 comes from — it all interacts with the oceans’ carbonate cycle in the same way.
Shoreline seawater pH is at the mercy of a stunningly huge number of real world factors — it is a natural interface “where all the action takes place” — and does not represent the greater ocean or its problems.
““where all the action takes place” — and does not represent the greater ocean or its problems.”
I think i would beg to differ on that last bit. Most species in the oceans reproduce there in mudflats, mangroves, sand, reefs and estuaries. Are there any species from the mid ocean that can’t live there? One would think that it does represent the greater ocean and its problems.
Reply to Eric H ==> Yes, and this is my point exactly. The natural hourly, daily, and seasonal fluctuations of pH in tide pools and the like are very large….but in mangroves, no so much…don’t know where you are from, but I have sat out a few passing hurricanes on my sailboat tied up in the mangroves — and there is not much water action and pH is believed to be pretty stable there. There is a lot of fish nursery going on though.
It is not strictly correct that “most species in the oceans reproduce there…” They are important nurseries for many species, but not for pelagic species. The vast majority of ocean biomass is out there in the open ocean.
Much of the concern for OA is in and around reef structures (because they are beautiful and attract and hold the attention of the public and press), which occur “mostly” near shore but not mostly in the very shallow tide pool range. Reefs are also important fish nurseries.
There is so much that we do not know about all this — and the only way to find out is proper, structure, correctly designed experimentation and research.
Part of the problem of scientists with laboratories and science toys is they are going to insist on using, or more likely are slaves of their craft, using what is familiar to them to design the experiment from the bottom up. Invariably, they get into confounding details. Lets, instead look at it as a non chemical engineering problem to see what might be designed. Let’s ask a mining engineer how he would design an experiment to determine the effect of OA on the seas. Without the seductive ‘cage’ of a laboratory he is free to think of the problem in a gross fashion that automatically takes all the tiny minutiae and confounding factors into consideration after he gets answers to a few defining questions:
Q: What is it that we should be worried about with OA?
A: We’re worrying about the ability of ocean creatures to thrive in a less alkaline environment.
Q So we are talking about ocean productivity, right?
1) The engineer as a first brush would go with creatures that don’t move around that much – shell fish. He would start with getting biologists to select 20 similar habitats of abundant shell fish in various parts of the world. Using a submersible, he would run photo traverses across each habitat from which would be estimated the population and weight of their calcium carbonate (a thing that should have been done 50 years ago if Scripps had asked a mining engineer for advice). Take samples of seawater at intervals of depth and across the habitat and estimate the habitat’s pH and water chemistry. And survey the plots for average T.
2) every two years, repeat and possibly every five years thereafter if the plot hasn’t detectably changed. Use these plots as standards forever.
3) Do calculations of the numbers of fish in much larger areas, defined by main fisheries locations. Probably the amount of fish caught annually are a good sample of the populations – also 18% of them are Carbon or equivalent to 65% of the catch weight is CO2!!! removed from the ocean! Wow even I didn’t know that!
4) Have cooperative exchanges with specialists on whales, coral, sharks, etc. Initiate regular surveys if these aren’t being done.
5) etc.
Gross productivity of the oceans measured in Carbon or Carbon Dioxide is all you need to determine if there is a developing problem. It takes care of the irreducible problems and minutiae of the chemistry of ionization of H2O/CO2, Boric acid, Chlorine/HCl, etc and confounding Ca/Mg concentrations. I took the 18% from human composition of C, so really we are walking 65% CO2 deposits, each and every one of us!
All quite interesting, beside the point, and so what. The points that matter:
1) IPCC AR5 has no idea how much of the CO2 increase between 1750 and 2011 is due to industrialized man because the contributions of the natural sources and sinks are a massive WAG. Hard to say whether the sudden appearance of 2.2 trillion trees helps or hinders.
2) The 2 W/m^2 RF that “unbalances” the global heat balance and that IPCC AR5 attributes to that CO2 increase between 1750 & 2011 is lost in the magnitudes and uncertainties of the major factors in the global heat balance, e.g. ToA (340 W/m^2 +/- 10 W/m^2), clouds (-20 W/m^2 +/-?), reflection, absorption, +/-, etc. CO2 is a third or fourth decimal point bee fart in a hurricane.
3) IPCC AR5 admits in text box 9.2 that their GCM’s cannot explain the pause/hiatus/lull/stasis probably because their climate sensitivity is incorrect, as acknowledged in TS.6, and the GCMs & RCPs 3.0, 4.5 6.0, 8.5 are consequentially useless.
Stay on target, Luke!
Having done a lot of experimental work I’m appalled that apparently even PhD. programs don’t include a course of experimental design. It’s amazing that the Cornwall and Hurd paper even needed to be done. Experiments done without design are simply money down the drain. The basic methods have been available since World War II. In fact the work of Ronald Fisher(one of the pioneers) was probably a top secret topic because it was undoubtedly used in improving things such as airplane engines, and weapons wirh great effectiveness.
The example given above in the article shows the power of the methods. Instead of using one step at a time methods which are time consuming and expensive, variables such as concentration, time, temperature are tested at two reasonable levels in 2^n trials. In this case 2^3 experiments(8). The variables in each trial are arranged(called blocking) so that in each trial all the variables have equal numbers of high and low levels are equally distributed. When analyzing the results each variable has four comparisons of its two levels. The multiple levels
make for much stronger statistical tests. One of Fisher’s contributions to this was a way of tabulating the experiments so that the analysis could be done with a mechanical adding machine to calculate the effect of a variable(and of all the interactions such as ab, bc, ac, abc), the standard deviation, and the f value and significance.
In the last 70 years with advances in statistical techniques and the computers needed to run the analysis the results are even better. The problems, as the sea water tests show, is not the mechanics of the experiments and analysis but in understanding how to best design the experiments and finding out how to actually run them appropriately.
Reply to Phil Carter ==> I mention the work being done at the University of Amsterdam on proper experimental design theory and practice for the social sciences. Other universities and programs are working on teaching experimental design. It is NOT easy, it is NOT straightforward, it takes a lot of foresight (and hindsight) to get it right especially in a new field of study. It is often a trade-off with available resources.
It is worse than we thought — guidelines were issued in 2010 for the OA field by EU’s EPOCA project. The sections seawater chemistry experimentation had traction and reduced errors from 21% to 3% by 2014, unfortunately the recommendations on experimental design and statistical analysis showed no such improvement in published research, so Cornwall and Hurd have taken another pass at it. Getting their paper highlighted in Nature was a stroke of luck as it will force much greater adherence to their recommendations.
(I will not be drawn into the scientists versus engineers thing…:-)
Fascinating listening to a ‘scientist’ talking about the effect of ‘ocean acidification’ on shellfish. This was on BBC radio 4 today and she was from Woods Hole and she explained they conduct these experiments by ‘bubbling CO2’ through the sea water in containers holding shellfish.
She went on to predict the dire effects they witnessed……
If I had run an experiment in that fashion at school then any of my science teachers would have heavily criticised me for an unscientific and meaningless experiment.
Kip,
I think the experiment that should be done is to design and perform and experiment when you have small pebbles of CaCO3 limestone scattered around the bottom of your large test sea water Aquarium (Sea world size or larger). Then add your organisms and other “local environment items” and make sure the creatures are still thriving a few months to a year later. Then increase the CO2 content to 500ppm above the Aquarium and see what happens. My bet is the pH at the bottom of the test Aquarium will stay at 8.2 and the creatures will either grow faster or no significant difference will be observed, If that is the case, the potential but highly unlikely future problem is solved. Just need to spread limestone pebbles around the handful of potentially sensitive areas around the globe. At roughly $10 a ton for limestone, you could spread a million tons around the sensitive areas for a mere $10million dollars.. super cheap fix and no one needs to give up their SUV.
Reply to alcheson ==> The first step is to discover whether or not there is a problem to so solved.
Research in this area includes naturally CO2-rich areas around sea floor CO2 vents, investigating the effects in the real worlds oceanic environment.
Simple buffering is not likely to be any more sensible than simply adding acid to the water to change pH.
I recommend reading the section of the EPOCA guidelines booklet on oceanic carbonate chemistry.
“whether or not there is a problem to be solved.”
Kip I have to disagree. Adding CO2 to water containing CaCO3 (sea water) actually increases its buffering capacity. Addition of CO2 increases both HCO3- and CO3–. This is easily demonstratable in the lab. Since CaHCO3 is not stable as a solid, the best way to prepare a solution of CaHCO3 is to bubble CO2 into water containing finely powdered CaCO3. As the CO2 dissolves in the water, the CaCO3 dissolves as well, resulting in a more concentrated buffer solution as ever more CO2 is bubbled in. The pH of this solution will remain at ~8.2 until all of the CaCO3 has dissolved. The solubility of CaHCO3 in water is about 18g/liter, much much higher than the concentration in sea water. To claim that CaCO3 pebbles dispersed on potentially sensitive sites would be no better than adding NaOH or H2SO4 to control the pH of sea water on shallow ocean floors is not a valid statement.
By the way, I would predict that increasing CO2 in the air would be beneficial to the ocean life, much like it is to plant life on the surface. Adding CO2 to sea water increases both HCO3- and CO3– levels in sea water if soluble forms of CaCO3 are available. CAGW and AGW types automatically assume it will have a negative effect. CO2 is necessary for current forms of life, both in the ocean and on land. Additional support for this likely beneficial notion is that the sea animals around when CO2 was very high tended to be very large and plentiful. Experiments to determine what the optimum CO2 levels would be might surprise the AGW types as it just could be somewhere between 1000 and 2000ppm, not near the bare minimum life supporting levels of 200ppm we were recently at.
Btw, I have a PhD in Inorganic chemistry so I am not a total novice when it comes to chemistry.
Best regards
Alcheson
Reply to Alcheson ==> As an expert, perhaps you will read the seawater carbonate section of the EPOCA booklet and let us know if you think they have it right.
If they have it incorrect, then they will simply waste more time, effort, and research funds.
Looking forward to your input on that.
[snip – waaaaaayyyyy off topic plus a policy violation – chemtrails discussion is prohibited here -mod]
Dang,,, and here I thought my Calif. lawn died because I turned the water off.
Dear – oh dear. I feel transplanted back to the mental hospitals of the 1950’s which were then full of people who earnestly believed that radio waves were the source of all the world’s problems.
Fred Zimmerman:
Ya know, good movements ALWAYS get co-opted and corrupted in time because loons get attracted to a s*** disturbing organizaton and begin to become silly as they go along as in the case of the nano particles of metal in the atmosphere and radio waves which we have been living with while our longevity is extending as we go along. A think tank that has little to do but sit around and think of stuff like the above is inevitable.
The fine 1960s ‘do your own thing’ was a boost to those a bit short on self esteem and infused some sense of belonging to a great supportive force. It got corrupted into the crisis of morality we have in society now, including the flagrant, rewarded dishonesty of the central clique of climate science. Probably the originators were rightfully concerned about all the talk of dumping millions of tonnes of fine iron fillings into the sea, or filling the stratosphere with sulphates (acid or acid generating) and even setting up enormous wind farms and solar farms. So far so good. But, when you have covered all the bases, then what do you do? You do stuff like Fred Zimmerman is reporting on. Usually they are not scientists but well meaning, easily swayed, concerned arts folks and they end up marginalizing and labeling themselves out of any place of influence. It’s always something that would cripple civilization, freedom and free enterprise and it is always something that won’t be changed. This wasted effort also becomes another tax-like burden to the rest of us.
Trees dying all over the planet
Jets dropping nano-particles?
And all that other nonsense you are spouting?
How do you reconcile this with the fact that people are living longer than ever, and doing so in better health, by far, than was ever before the case.
For what it is worth…none of the things you are frightened of are real.
Trust me.
Go for a swim. Or a bike ride.
It’ll do wonders for ya.
This issue should be pretty easy to resolve. There are X Gallons of water in the oceans, there is Y buffering capacity and pH is determined by the quantity of CO2 dissolved in that quantity of water.
http://ion.chem.usu.edu/~sbialkow/Classes/3650/Carbonate/Carbonic%20Acid.html.
To measure the extremes of the change one would simply take a gallon of sea water and fill the space above the H2O with 100% CO2.
Bottom line, there are huge volcanoes that continually spew CO2 from the ocean floor and they have no real impact on sea life or the pH of the ocean. Calciferous plankton and algae gobble up aquatic CO2 providing natural buffering and carbon sequestration systems. Atmospheric CO2 used to be 7000 PPM and the result was thriving sea life and the great reefs. We have millions of years of history to study the impact of high CO2 levels on ocean pH and none of it will show CO2 causing catastrophic effects to sea life.
http://edberry.com/SiteDocs/2010/10/EarthHistory1.jpg
From http://coral.aims.gov.au/info/reefs-palaezoic.jsp
The first reef-like structures of animal origin were built by archaeocyath sponges of the Lower Cambrian (530-520 million years ago). What reef-building there was after the extinction of the archaeocyaths was mostly due to cyanobacteria, stromatolites and some coral-like Anthozoa, all growing in shallow protected waters and containing abundant trilobites together and a wide diversity of molluscs.
[atmospheric C02 4600 to 7000ppm].
Late Cambrian ecosystems persisted into the Middle Ordovician, when complex algae and invertebrate reef communities became widespread and reef biota greatly diversified. Stromatoporoid sponges and tabulate corals radiated at this time. Rugose corals first appeared in the Middle Ordovician and rapidly increased in number and diversity. Thus, algal communities were largely replaced by communities of skeletonised metazoans. By Late Ordovician, colonial rugose and tabulate corals had greatly diversified in shallow water and formed coral patch reefs, along with stromatoporoids other sponges and calcarious red algae. These reefs had little wave resistance and did not form solid platforms although stromatoporoids and tabulate corals formed massive colonies several meters diameter. These are the oldest-known reef coral communities and were possibly the outcome of symbiotic animal/algal associations.
[atmospheric C02 4100 to 4500ppm]
For at least 150 million years different combinations of these algae, sponges and corals built reefs around the tropical world. Silurian reefs became abundant and diverse and some reached massive proportions, the first truly wave-resistant carbonate platforms.
[atmospheric C02 3000 to 4400ppm]
Or in the lab you can bubble some CO2 through a bath with a few mussels in it
The failing of of commercial oyster beds near Oregon – I have read that the oysters used are not native oysters derived from Japanese oysters introduced to Oregon in recent decades. Interestingly, the few native oysters still living there were not affected by the changing ocean characteristics and experienced no ill effects. I know what it says to me. Rather than trying to make CO2 a pollutant, why not use this money to stop overfishing or fixing Fukushima which is still throwing hundreds of tons of radioactive water into the Pacific every day and has been since the beginning of the accident. They still don’t even know where the melted cores are located and by now are outside the containment.
Reply to Jim Payette ==> See Bob Highland’s comment above for the full whiskey Creek oyster story. He gives a link to the final chapter—-It turned out not to be pH that was at the root of the problem.
Jim
How did you get to oyster beds in Oregon to damaged reactors in Japan? I have a pretty idea of idea where most of the damaged cores are, inside the reactor vessel. Some of the damaged fuel has been released to the reactor coolant system. Since relief valves lifted, some of the reactor coolant ended up in the suppression pool which is inside containment. Since the containment was vented after evacuation occurred, some of the fission products were released but no one was hurt.
Furthermore there was no environmental damage. Plants and animals do not have an irrational fear of radiation. Jim makes up a story in his head and enjoys the drama. Since I have a great deal of experience with those designs, I watched closely to see what lessons could be learned and that models of severe accidents were validated that robust designs protected people.
not native oysters but derived
“Regardless of the degree of precision that the treatment is applied and its effects measured, if treatment effects are confused with the effects of other factors not under investigation, then an accurate assessment of the effects of the treatment cannot be made.”
Simply put. A+B=27. While Claiming to know the properties of 14, you ignore 13. Assuming, of course, that you figured out 14. Nooooooo ProbLAYmo! Just make it sound sciencey, and scary. Grant money will flow…an nobody will be any wiser.
My guess, and I’ll claim it as an informed guess, but not much more than that,, is that, even with significant acidification, very few species will be really challenged, though the balance of species in any given location may change. There are several reasons for this –
(1)Local, regional, seasonal, and temporal (even daily)variations in pH are much larger, often by an order of magnitude, than projected global changes. This is especially so in continental and coastal waters which are the subject of most concern to fisheries and shallow-water ecosystems.
(2)Every species will react differently, but there is already a huge and resilient genetic diversity, even between different populations of the same species, to suggest that effects will be quite minor.
(3)The fecundity of almost all of the carbonate shell forming organisms is unimaginably large – millions and up per individual- that we may expect a very rapid evolutionary response to selective pressures (certainly well within the timescale of an ongoing acidification). For this reason, short-term experiments in tanks will be quite unable to capture the diversity, or the resilience, of the organisms studied.
But, as you can see, it provides a career for quite a few scientists (465 papers analysed?) to play around anyway..
What ever happened to “Acid Rain”. I haven’t heard about acid rain since childhood.
Reply to Ryan ==> The EPA still has a major section on acid rain on its website. It is recently less popular with the MSM which no longer finds it scary enough.