Friday, October 17, 2014

New paper debunks "acidification" scare, finds warming increases pH

A paper published today in Climate of the Past reconstructs water pH and temperature from a lake in central Japan over the past 280,000 years and clearly shows that pH increases [becomes more basic or alkaline] due to warmer temperatures, and vice-versa, becomes more acidic [or "acidified" if you prefer] due to cooling temperatures. This finding is the opposite of the false assumptions behind the "ocean acidification" scare, but is compatible with the basic chemistry of Henry's Law and outgassing of CO2 from the oceans with warming. 

Thus, if global warming resumes after the "pause," ocean temperatures will rise along with CO2 outgassing, which will make the oceans more basic, not acidic. You simply cannot have it both ways:
"Either the oceans are getting warmer and the CO2 concentration in seawater is decreasing, which means that ocean acidification from man-made CO2 from the atmosphere is nonsense. 
Or the oceans are getting cooler and the man-made CO2 from the atmosphere is dissolving in those cooler oceans and causing – insignificant – ocean acidification, which means that warming oceans and the associated sea level rises are nonsense. 
Take your pick – REAL SCIENCE says you can’t have both."
In addition, the paper shows that pH of the lake varied over a wide range from ~7.5 to 8.8 simply depending on the temperature of each month of the year. As the "acidification" alarmists like to say, a variation of 1.3 pH units is equivalent to a 1995% change in hydrogen ions due to the logarithmic pH scale, just over a single year! Summer months are of course associated with warmer temperatures and more alkaline, higher pH and winter months associated with colder temperatures and much more "acidified" lower pH values. Note also how pH varies widely over ~7.5 to 8.8 simply dependent on the depth at a given time, because colder deeper waters can hold higher partial pressures of CO2 than the warmer surface waters:



Second graph from left shows reconstructed pH over the past 280,000 years, third graph from left shows temperature reconstruction. Note how these move in sync, although the paper says pH lags temperature sometimes by up to several thousand years, i.e. just like CO2 lags temperature in the ice core records also by about 1000 years. 
"Comparison with pollen assemblage in Lake Biwa cores suggests 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."
These findings completely contradict the basis of the CAGW "acidification" scare and instead show that warming should make the oceans more alkaline, not "acidic."

UPDATE: Some have claimed that the pH does not "acidify" with increasing depth/decreasing temperature in the oceans, debunked by the World Ocean Circulation Experiment data below showing a variation of ~0.4C pH units from the surface to the "acidified" colder depths below:



Clim. Past, 10, 1843-1855, 2014
www.clim-past.net/10/1843/2014/
doi:10.5194/cp-10-1843-2014



T. Ajioka1, M. Yamamoto1,2, K. Takemura3, A. Hayashida4, and H. Kitagawa5
1Graduate School of Environmental Science, Hokkaido University, Kita-10, Nishi-5, Kita-ku, Sapporo 060-0810, Japan
2Faculty of Environmental Earth Science, Hokkaido University, Kita-10, Nishi-5, Kita-ku, Sapporo 060-0810, Japan
3Institute for Geothermal Science, Kyoto University, Noguchihara, Beppu, Ohita 874-0903, Japan
4Department of Environmental Systems Science, Doshisha University, 1–3 Tatara-Miyakodani, Kyotanabe, Kyoto 612-0321, Japan
5Graduate School of Environmental Studies, Nagoya University, Nagoya 464-8601, Japan

Abstract. 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.


Related: 

New paper finds global carbon cycle datasets may be biased

22 comments:

  1. So they correlated precipitation and temperature to pH. Separate study would be needed to correlated their pH to CO2 content of the air.

    There is also the vegetation to think of: a pine forest produces acidic soils, so more pine forests give more acidity (think the Pine Barrens of New Jersey, where the acidity of the runoff created the bog iron deposits that built America until the Lake Superior banded iron deposits and blast furnaces changed the iron industry). Less pine forests, less acidity, i.e. increased pH value.

    A lake could be useful for pH vs CO2, but it would not be simple, unless it was big enough to negate vegetation/runoff effects. Glacial cycles are big enough to change source water, too, so that would have to be taken into account.

    Not as simple as one might think.

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  2. I always wondered whatever happened to Henry's Law. Alarmists had thrown it out of their window it seems. Why don't they do the same with the Law of Gravity and take a long walk on a short plank hanging over a cliff?

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  3. Shock Horror! Global warming causing oceans to become more alkaline!

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  4. The oceans also have an enormous sink of calcium carbonate.

    This will be at equilibrium with the ocean pH, and as such is one HUGE buffer.

    It is obvious the pH of the world's oceans is inherently stable.

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    Replies
    1. True and there is far more CaCO3 in the oceans than this lake, more than enough to completely buffer CO2 from burning all stores of fossil fuels

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  5. Anyone that maintains a swimming pool should already know this. Whenever temperatures rise, so does the pH, and vice versa. This is a no brainer...

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  6. Whatever causes "warmest" or "coldest" or "highest level of ice cover in Antarctica since records began" it is not carbon dioxide.


    If a molecule has an upward component in its free path movement between collisions then some of the translational kinetic energy in that molecule (M.Cp.dT) supplies the additional gravitational potential energy (M.g.dH) that it acquires by virtue of its additional altitude. Vice versa for downward motion. Equate the two and you have the temperature gradient dT/dH = g/Cp which should not be hard to understand.

    Because the laws of physics can be used to explain this gravitationally induced temperature gradient, the fact that the surface temperature of a planet is higher than the radiating temperature of the planet is fully explained (and confirmed empirically) by this autonomous temperature gradient.

    There is thus no need for any other explanation as is supposedly presented in the false radiative greenhouse conjecture.

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  7. Any person with common sense knows that carbonated beverages (soda pop) go "flat" if they are allowed to warm up. The warming causes the CO2 to leach out into the air above the fluid and under the sealed cap. Same with the oceans.

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  8.  

    Carbon dioxide actually causes Earth’s surface temperature to be very very slightly cooler, whilst water vapour has a significant cooling effect of about 10 to 12 degrees. This is because their radiating properties reduce the magnitude of the gravitationally-induced temperature gradient that is the state of thermodynamic equilibrium which the Second Law of Thermodynamics tells us will evolve spontaneously as entropy approaches a maximum.

    On all planets temperatures in any troposphere get hotter as you approach the base of that troposphere, whether or not there is a surface there, whether or not solar radiation reaches the lower troposphere and quite regardless of whether there is carbon dioxide or water vapour in the planet’s atmosphere.

    There is absolutely no empirical evidence and no valid physics that you can produce which supports the ludicrous concept that radiation from colder regions in the troposphere produces more thermal energy to be transferred by radiation into a planet’s surface than entered the atmosphere at its top. But that is precisely what the K-T and IPCC energy diagrams claim to be the case on Earth.

    Believe it if you’re that gullible!

     

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    Replies
    1. Ok if CO2 has cooling effect why is Venus hotter than Mercury?

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    2. 93 bars pressure on Venus at the surface

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  9. Sorry, but wrong title:

    - The pH changes in a fresh water lake are completely unrelated to pH changes in seawater.
    - Henry's law still is in full force, but says that for a given temperature the amount dissolved is directly proportional to the partial pressure of the gas in the atmosphere.

    The influence of temperature is ~0.0114 pH unit per °C. As 1°C is about the maximum warming since the LIA, that is all what can be expected of warming oceans. See:

    http://wap.aslo.org/lo/toc/vol_14/issue_5/0679.pdf

    The warming of the oceans changes the equilibrium with the atmosphere with ~8 ppmv/°C. The real increase since 1850 is ~110 ppmv.
    That means that more CO2 is pressed into the oceans, not reverse. Which is measured in 4 long term series and lots of more sporadic/regular sea ships measurements over time.
    Here Fig. 5 from Bermuda:
    http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
    and Fig. 1 from Hawaii:
    http://www.pnas.org/content/106/30/12235.full.pdf

    Thus sorry, the article doesn't debunk anything...

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  10. Hi Ferdinand,

    "The pH changes in a fresh water lake are completely unrelated to pH changes in seawater."

    Not true, temperature dominates over pCO2 to control solubility in both seawater and fresh water.

    "Henry's law still is in full force, but says that for a given temperature the amount dissolved is directly proportional to the partial pressure of the gas in the atmosphere."

    Temperature dominates over pCO2 changes as the primary driver of Henry's Law as clearly shown by fig 1 and 2 above. Fig 2 covers 2 glacial-interglacial cycles and shows T drives Henry's law and CO2 outgassing on a long-term timescale. Fig 1 shows T drives Henry's Law on a month and daily basis, showing solubility of CO2 changes not only with monthly surface temperature, but daily dependent upon temperature at various thermoclines.

    "The influence of temperature is ~0.0114 pH unit per °C. As 1°C is about the maximum warming since the LIA, that is all what can be expected of warming oceans. "

    As shown by fig 1 above, a ~7C cooling is associated with a ~0.8 pH "acidification," about an order of magnitude higher than you are claiming.

    "Thus sorry, the article doesn't debunk anything..."

    Yes it does, for the reasons set forth above.

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  11. There are lots of differences between what happens in a fresh water lake and what happens in the oceans:

    The solubility of CO2 in fresh water decreases with ~5% for a temperature increase from 15 to 16°C:
    http://www.engineeringtoolbox.com/gases-solubility-water-d_1148.html
    The solubility of CO2 in seawater changes with less than 1% for the same temperature change. See Fig. 2 in:
    http://my.net-link.net/~malexan/Appendix%20B.htm
    That is because the solubility of CO2 remains the same for both cases per Henry's law, but free CO2 is only 1% in seawater. The rest are (bi)carbonates which don't play a direct role in CO2 partial pressure, but do react on free CO2 changes.
    The solubility of CO2 in seawater is also much higher than in fresh water.

    pH changes in fresh water can be huge and at CO2 saturation, the pH of the solution is between 4 and 5. Any change in CO2 due to temperature can have a huge effect. As the change in solubility is high in fresh water, the effect is high on pH too. For seawater, again the effect of temperature on CO2 levels is way smaller and the effect of changes in CO2 concentration on pH changes is also a lot smaller because of the buffer effect of the solution.

    Thus again what happens in a fresh water lake with very little buffer capacity and much less CO2 in solution is not comparable to what happens in the oceans...

    Further, have a look at the seasonal changes of pH in the ocean surface of Bermuda:
    http://www.biogeosciences.net/9/2509/2012/bg-9-2509-2012.pdf
    in figure 4 the seasonal temperature change is 8°C while the accompanying change in pH is ~0.1 unit. Compare that to the 0.8 pH unit change in the fresh water lake for near the same temperature change...

    Thus definitively fresh water lakes and oceans are not comparable for their reactions on changes in CO2, pH, temperature, etc.

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    Replies
    1. Ferdinand,

      I agree that "any change in CO2 due to temperature can have a huge effect" and that temperature dominates over atmospheric pCO2 to determine dissolved pCO2.

      The ocean does of course have nearly unlimited buffering capacity and your 2nd link is just absolutely false to claim "Apparently, the ocean is not strongly buffered." Thus, the effect of temperature is smaller than for a lake, but nonetheless still dominates over atmospheric pCO2 to control solubility and dissolved pCO2 levels. The huge ocean buffering capacity, more than enough to accommodate burning of all stores of fossil fuels, along with decreased solubility with warming, both debunk the "acidification" scare.

      Delete
  12. Another HS comment at WUWT:

    http://wattsupwiththat.com/2014/10/21/new-paper-debunks-acidification-scare-finds-warming-increases-ph/#comment-1770659

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

    This is false because as figure 1 above shows, pH and dissolved pCO2 stratify by layer, with pCO2 increasing and pH decreasing according to the temperature at various thermoclines. Temperature dominates over changes in pCO2 to control water pH levels by thermocline. Figure 1 shows a huge 1.3 pH variation over the top 20 meters clearly controlled by temperature, not well-mixed CO2 levels.

    The fact that the ocean has essentially unlimited buffering capacity means that the change in pH due to temperature/solubility will be less than in a freshwater lake, but nonetheless, ocean pH measurements clearly show wide variation of .35 pH units over a few days from the same thermocline, as compared to this paper finding a variation of ~1.3pH units over monthly resolution in a lake reconstruction. But, the important point is the sign of change is the same and temperature still dominates over pCO2 levels to control pH.

    http://stevengoddard.files.wordpress.com/2011/07/monterey_bay_ph.png

    The Monterey Bay Pacific Ocean data also shows no pH trend.

    Here's a paper debunking the comments here claiming that the same Henry's Law relationship is not found in the oceans as in this lake, as this paper's data is from the Pacific Ocean and finds the exact same relation:

    "Ī©arag [aragonite buffer] and pH decrease rapidly with depth, such that the saturation horizon is reached already at 130 m"

    http://hockeyschtick.blogspot.com/2013/06/new-paper-finds-no-evidence-of-ocean.html

    Clearly, both lakes and oceans stratify pH and pCO2 dissolution nearly instantly by temperature thermoclines, although the effect is less in the oceans due to much greater buffer capacity. Therefore, temperature dominates over well-mixed CO2 to control solubility and hence pH levels.

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  13. http://www.science-skeptical.de/wp-content/uploads/2014/10/6a00d83452403c69e2013486431a89970c.jpg

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  14. http://www.pmel.noaa.gov/pubs/outstand/feel2331/images/fig01.jpg

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  15. http://www.whoi.edu/OCB-OA/page.do?pid=112157

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  16. Considering that CO2 levels were 5 times as high as today (2,000 ppm) 250-100 million years ago (Triassic, Jurassic, Cretaceous ages), and that marine life actually evolved and then continued to thrive and develop during these very-high CO2 periods, how is it that the oceanic biosphere was able to do so (evolve, thrive) back then if CO2 levels that are now 80% lower (400 ppm) are said to be causing unquenchable and fatal acidic harm?
    ---------
    http://onlinelibrary.wiley.com/doi/10.1029/2006GL0...
    [T]here would not be accentuated changes in either seawater salinity or acidity from the observed or hypothesized rises in atmospheric CO2 concentrations.
    ---------
    http://www.sciencedirect.com/science/article/pii/S...
    Recently ocean acidification as a major threat for marine species has moved from a consensus statement into a much discussed and even challenged conception. A simple meta-analysis...[indicates that] marine biota may turn out to be more resistant than hitherto believed.
    ---------
    http://www.sciencedirect.com/science/article/pii/S...
    Ocean acidification has been proposed to pose a major threat for marine organisms...Here we show, on the basis of meta-analysis of available experimental assessments, differences in organism responses to elevated pCO2 and propose that marine biota may be more resistant to ocean acidification than expected.
    ---------
    http://www.nature.com/ismej/journal/v6/n9/full/ismej201219a.html
    We found that pH did not have a significant impact on the composition of associated microbial communities in both coral species. In contrast to some earlier studies, we found that corals present at the lower pH sites exhibited only minor physiological changes and no microbial pathogens were detected. Together, these results provide new insights into the impact of ocean acidification on the coral holobiont.
    ---------
    http://onlinelibrary.wiley.com/doi/10.1111/j.1365-2486.2009.01955.x/abstract
    Despite increasing scientific and public concerns on the potential impacts of global ocean warming on marine biodiversity, very few empirical data on community-level responses to rising water temperatures are available other than for coral reefs. Plant and animal communities at 136 rocky reef sites around Tasmania (south-east Australia) were censused between 1992 and 1995, and again in 2006 and 2007. Despite evidence of major ecological changes before the period of study, reef communities appeared to remain relatively stable over the past decade. We suggest that our study encompassed a relatively stable period following more abrupt change, and that community responses to ocean warming may follow nonlinear, step-like trajectories.
    ---------
    http://www.nature.com/nclimate/journal/v2/n8/full/nclimate1473.html
    Using a model of pH regulation combined with abiotic calcification, we show that the enhanced kinetics of calcification owing to higher temperatures has the potential to counter the effects of ocean acidification.
    ---------
    http://onlinelibrary.wiley.com/doi/10.1029/2004GL021541/abstract
    Our results suggest that present coral reef calcification rates are equivalent to levels in the late 19th century and does not support previous suggestions of large and potentially catastrophic decreases in the future.
    ---------
    http://multi-science.metapress.com/content/c6481l4677j11333
    The supposedly already-degraded state of coral reef ecosystems is sometimes claimed to be a reason why anthropogenic global warming will have a major impact on the reefs, i.e. they are already close to extinction and can easily be tipped over the edge. It is concluded that the work of Pandolfi et al. (2003) cannot be used as justification that the Great Barrier Reef has lost significant resilience, or that it is particularly susceptible to global warming because of its present supposedly degraded state.

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  17. Apologies. Here are the *un*broken links for the first 3 papers referenced above...

    http://onlinelibrary.wiley.com/doi/10.1029/2006GL026305/abstract
    [T]here would not be accentuated changes in either seawater salinity or acidity from the observed or hypothesized rises in atmospheric CO2 concentrations.

    http://www.sciencedirect.com/science/article/pii/S0272771410002167
    Recently ocean acidification as a major threat for marine species has moved from a consensus statement into a much discussed and even challenged conception. A simple meta-analysis...marine biota may turn out to be more resistant than hitherto believed.

    http://www.sciencedirect.com/science/article/pii/S027277140900537X
    Ocean acidification has been proposed to pose a major threat for marine organisms...Here we show, on the basis of meta-analysis of available experimental assessments, differences in organism responses to elevated pCO2 and propose that marine biota may be more resistant to ocean acidification than expected.

    ReplyDelete
  18. It has been claimed that the primary reason why “ocean acidification” due to higher CO2 levels will cause mass-extinctions of the oceanic biosphere in the near future, though it didn’t during past climates (when CO2 levels were 2,000 ppm or more), is because the 20th/21st century increase in CO2 concentration (from 300 ppm to 400 ppm) is “unprecedentedly” rapid. Corals, it's claimed, just can’t handle so fast an increase (100 ppm in 100 years) in CO2 levels. But yet, according to this paper (below), when corals were assessed for response to exponentially increasing concentrations of CO2 (from 285 ppm to 4,568 ppm) over a 4 week period, the authors found that "growth and calcification did not stop in any of the concentrations of pCO2.” Again, in 4 weeks, CO2 concentrations were raised from 285 ppm to 4,568 ppm---which is orders of magnitude more rapid of an increase than the atmospheric 300 ppm to 400 ppm rise during the last 100 years---and yet this did not affect coral growth and calcification rates. The authors could therefore conclude that corals “could still survive well in mid-term ocean acidification conditions expected by the end of this century.”
    ----------------------------------------------------------
    http://link.springer.com/article/10.1007%2Fs00338-014-1241-3

    "This study investigated the response of the gorgonian coral Eunicea fusca to a range of CO2 concentrations from 285 to 4,568 ppm (pH range 8.1–7.1) over a 4-week period. Gorgonian growth and calcification were measured at each level of CO2 as linear extension rate and percent change in buoyant weight and calcein incorporation in individual sclerites, respectively. In general, growth and calcification did not stop in any of the concentrations of pCO2… These results highlight the susceptibility of the gorgonian coral E. fusca to elevated levels of carbon dioxide but suggest thatE. fusca could still survive well in mid-term ocean acidification conditions expected by the end of this century, which provides important information on the effects of ocean acidification on the dynamics of coral reef communities."

    ReplyDelete