Anthony Watts (and others) fail ocean chemistry - woefully!

I noticed Anthony Watts retweeted something the other day and wondered if he'd be dumb enough to copy and paste it at WUWT.

He is and he did.

Anthony loudly proclaims his ignorance of basic physics and chemistry, with the headline:

New paper debunks ‘ocean acidification’ scare, finds warming increases pH

He copied his article (archived here) from another denier blog that often makes scientific bloopers, the Hockeyschtick.


This leads me to the twitter exchange I saw. It went like this. First up Marc Morano tweeted about the HockeySchick dud article, and Seth Borenstein replied:

@ClimateDepot Its CO2 chemical reaction not hot temps acidfies ocean http://t.co/gVxfFWxZoy http://t.co/RfRyJsWt2h. Chemistry what a concept
— seth borenstein (@borenbears) October 17, 2014

.
Then the HockeySchtick mumbled something about Henry's Law and Anthony Watts showed his profound ignorance.

@hockeyschtick1 @borenbears @ClimateDepot holy crap I can't believe Seth said that. Solubility vs. Temperature. No chemistry needed.
— Watts Up With That (@wattsupwiththat) October 18, 2014

Sheesh! And some people seriously think they'll learn science from science deniers?

I know I don't need to explain the multiple bloopers to you, but I will anyway, because you never know when a stray WUWT reader will happen here by accident or good fortune. It's really quite simple.

Freshwater lakes aren't the ocean

The first blooper is that the paper in question was about a freshwater lake. That can't be used to "debunk" anything about ocean acidification. The chemistry is quite different in freshwater to sea water. (The bonus blooper here was that the paper doesn't appear to have been about CO2, in the main.)

Solubility of a gas in a liquid

The second blooper relates to Anthony Watts not understanding solubility of a gas in a liquid. The amount of dissolved gas in a body of water is, in part, dependent on partial pressure and temperature. In an ideal situation, this is described in Henry's Law:

"At a constant temperature, the amount of a given gas that dissolves in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid."

Or, to put it another way, as temperature increases, to maintain the same amount of the gas dissolve in the liquid, the partial pressure of the gas must also increase.

Now the ocean doesn't behave as water would in a closed system in a laboratory where the temperature and pressure can be controlled. There are lots of other things happening, like waves and currents and wind. Just the same, if CO2 wasn't increasing and the oceans were warming, they'd emit CO2. That's what happened in the past when ice ages ended. The oceans warmed up, released CO2 which caused the earth (and oceans) to warm up even more. Eventually a new equilibrium was reached.

Today we're increasing the partial pressure of CO2 faster than the oceans can keep up with. So while the oceans are warming, they continue to absorb CO2. A lot of what we're pouring into the air is dissolving in the oceans.

Ocean acidification is chemistry

The third blooper relates to Anthony confusing the chemistry of ocean acidification with the solubility of gaseous CO2 in sea water. Dissolved CO2 reacts chemically with water. It's the chemical reactions that cause the pH to drop. Seth Borenstein was correct and Anthony Watts is a goose.

The equations look like this diagram attributed to the University of Maryland (I couldn't find the original):

Here's another explanation and diagram from NOAA's PMEL Carbon Program:

This process has made the sea 30 percent more acidic than it was before industrialisation. That's affecting the organisms that live in the sea, some more than others.

There is a lake in Japan

The paper that HockeySchtick found was published in Climate of the Past, and is open access. It had the title:

Water pH and temperature in Lake Biwa from MBT'/CBT indices during the last 280 000 years

The abstract (my paras):

We generated a 280 000 yr record of water pH and temperature in Lake Biwa, central Japan, by analysing the methylation index (MBT′) and cyclisation ratio (CBT) of branched tetraethers in sediments from piston and borehole cores.

Our aim was to understand the responses of precipitation and air temperature in central Japan to the East Asian monsoon variability on orbital timescales.

Because the water pH in Lake Biwa is determined by phosphorus and alkali cation inputs, the record of water pH should indicate the changes in precipitation and temperature in central Japan. Comparison with a pollen assemblage in a Lake Biwa core suggests that lake water pH was determined by summer temperature in the low-eccentricity period before 55 ka, while it was determined by summer precipitation in the high-eccentricity period after 55 ka. From 130 to 55 ka, the variation in lake pH (summer precipitation) lagged behind that in summer temperature by several thousand years.

This perspective is consistent with the conclusions of previous studies (Igarashi and Oba, 2006; Yamamoto, 2009), in that the temperature variation preceded the precipitation variation in central Japan.

Yes indeed. I can see you nodding your head and saying to yourself "Hmm, makes sense". Do you know the chemistry and biology involved in analysing the methylation index and cyclisation ratio of branched tetraethers in sediments from piston and borehole cores? If so, I'll let you explain it :)

I can but barely follow the science described in the paper. I'd have to do quite a bit of reading and go back and relearn a lot of chemistry, biochemistry and biology to understand half of what the paper is about. The introduction provides some context for the research (my paras):

The East Asian monsoon governs the climate of East Asia (Wang et al., 2003), and East Asian monsoon variability on orbital timescales has been the topic of many studies, which have revealed that it has responded to precession; however, the timing of monsoon variability continues to be debated.

Kutzbach (1981) hypothesised that the Asian monsoon responds to insolation changes at low latitudes, which are regulated by precession. According to this hypothesis, the summer monsoon is maximal when Northern Hemisphere summer insolation is maximal in the precession cycle. Indeed, oxygen isotope records from cave stalagmites in China have demonstrated that summer monsoon variability was pronounced at the precession cycle and maximal at the July–August precession (e.g. Wang et al., 2001, 2008; Yuan et al., 2004; Dykoski et al., 2005).

However, some proxy records are not consistent with this hypothesis. Clemens and Prell (2003) reported that Indian summer monsoon variability showed both precession and obliquity cycles and was maximal at the November perihelion on the precession band.

The pollen record in the north-western Pacific off central Japan shows that the East Asian monsoon has been strongest at the October–November perihelion in a precession cycle (Heusser and Morley, 1985; Igarashi and Oba, 2006). Thus, the conclusions have varied according to the proxy record used. 

Since the conclusions of different studies varied, the scientists embarked on their own research. They described the factors affecting pH of lakes in general as:

1. the geology of the drainage basin,
2. evaporation, 
3. the photosynthesis of phytoplankton and submerged plants, 
4. the respiration of organisms, and 
5. the decomposition of organic matter by microbes. 

The paper goes into a lot of detail describing the different factors determining pH in this particular lake. From that information, they then worked out how pH was determined in different orbital periods, looking back over the past 280,000 years. If you are tuned into the subject, you'll probably find the details interesting reading. It really didn't seem to be about atmospheric CO2, or not directly anyway. There was some discussion of how today, in the particular lake being studied, Lake Biwa, photosynthesis is controlled mainly by the phosphorus concentration. The pH increased by more than 1 from the 1960s to the 1970s, from agricultural runoff after rain, which is rather a lot. (Fresh water doesn't have the buffering capacity of sea water.) From that they deduced that "summer precipitation in the watershed is a factor that controls photosynthesis and, consequently, the pH of the lake water". Then they discussed the effect of chemical weathering and more. It was highly technical and I won't try to explain the ins and outs, not least because I don't understand it.

The upshot is that the scientists suggested that:

Lake water pH was determined by summer temperature in low-eccentricity periods, while it was determined by summer precipitation in high-eccentricity periods. From 130 to 55 ka, variation in lake pH (summer precipitation) lagged behind that in summer temperature by several thousand years. Thaumarchaeotal production was enhanced in specific periods in interglacials. 

And if you are practically dying of curiosity:

The Thaumarchaeota (from the Greek 'thaumas', meaning wonder) are a phylum of the Archaea proposed in 2008 after the genome of Cenarchaeum symbiosum was sequenced and found to differ significantly from other members of the hyperthermophilic phylum Crenarchaeota.[1][2] Three described species in addition to C. symbosium are Nitrosopumilus maritimus, Nitrososphaera viennensis, and Nitrososphaera gargensis.[2] All organisms of this lineage thus far identified are chemolithoautotrophic ammonia-oxidizers and may play important roles in biogeochemical cycles, such as the nitrogen cycle and the carbon cycle. 

Well, there you go. You (might have) learnt something today :)

From the WUWT comments

It's interesting to see if WUWT readers are more scientifically literate than Anthony Watts, the HockeySchtick and Marc Morano. Many of them are, you'll be pleased to learn. Too many are not. First some of the crass and ignorant comments.

Eric Worrall 

October 21, 2014 at 12:40 am
The ocean acidification scare was always going to be a crock. The outgassing from any warming of the ocean utterly swamps any uptake due to higher CO2 concentrations in the air. Nice to see some measurements which confirm this basic science.

Konrad won't accept science. Not now. Not ever.

October 21, 2014 at 2:36 am
Sorry Ferdinand, it just won’t do. It is as Viscount Monckton wrote – “ocean “acidification” is the last refuge of the global warming scoundrel.”
Why “acidification” as opposed to the more accurate “de-alkinisation”? Because “acid” sounds ever so much scary, doesn’t it? You and yours chose propaganda over science and were fool enough to do so while the Internet kept a permanent record.
There can be no forgiveness. Not now. Not ever.

There were a few people who made informed comments:

James

October 21, 2014 at 12:43 am
And what about the partial pressure component of Henry’s Law?
“At a constant temperature, the amount of a given gas that dissolves in a given type and volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid.”

The increases in partial pressure is a lot more than the temperature rise. The overall affect will be decrease in pH in Oceans. 

Jerker Andersson  (extract)

October 21, 2014 at 1:01 am
I think we should not mix up what has happened during the last 280k years with what is happening now when it comes to CO2. While Henrys law says that a warm oceans can disolve less CO2 than a cold oceans it also says that if you increase the partial pressure of the CO2 in the atmosphere there will be an imbalance and the iceans will start to disolve CO2 from the atmosphere until a new equilibrium is reached. When that has happened both the oceans and the atmosphere has a higher amount of CO2.

Mike Jonas

October 21, 2014 at 1:17 am
Jerker Andersson is right. In the past, as stated in the paper, atmospheric CO2 and its balance with the oceans was all natural and the warmer = more alkaline relationship applied. But today, atmospheric CO2 has been increased by fossil fuel usage etc, and that pattern has been disturbed. It does seem clear that ocean pH has decreased very slightly in recent years, and that man-made CO2 is one of the factors. Doesn’t justify alarmism, though. 

Mostlyharmless  

October 21, 2014 at 1:59 am
“Not so fast…” indeed – claiming that a study of pH changes in a freshwater lake proves or disproves anything at all wrt so-called “ocean acidification” is very reminiscent of warmist “tricks”, and has no place on a truly sceptical blog. Citing Henry’s law is also invalid, as sea-water chemistry is complex, and pH is heavily buffered.

tty

October 21, 2014 at 3:00 am
Unfortunately this has absolutely no relevance for “ocean acidification”. The chemistry of freshwater lakes is very different from oceans.

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Ajioka, T., M. Yamamoto, K. Takemura, A. Hayashida, and H. Kitagawa. "Water pH and temperature in Lake Biwa from MBT'/CBT indices during the last 280 000 years." Climate of the Past 10, no. 5 (2014): 1843-1855. doi:10.5194/cp-10-1843-2014