Contributions of a plasma physicist to carbonate geochemistry and paleoclimatology The legacy of Tom Wigley

Niel Plummer U.S. Geological Survey Reston, VA

Symposium in Honor of Tom M. L. Wigley 19 June 2009 NCAR Mesa Lab Main Seminar Room 1850 Table Mesa Drive, Boulder, CO 80305 USA

Tom on calcite kinetics and geomorphology of caves, 1974. One of the problems with coming from Australia is that one tends to see things upside down. Maybe it is higher temperature which is needed to get into the intermediate region. Lower temperature is what I want subconsciously to explain caves, scallops, etc.features which are hard to explain unless diffusion plays a part.

Example of notes developing theory in Plummer and Wigley, 1976

TML Wigley, ca 1975

I have revised the paper (again) and re-titled it The effect of dissolution kinetics on the mating call of the lesser spotted grebe. I hope you approve. We could submit to Geochimica Cosmochimica Acta perhaps. And then try to claim a world record for the most revised paper..
TMLW, 24 March, 1975.

Calcite I

I am just surfacing from the depths of a cooling tower which has been my home for the past 6 weeks. Actually my home has only been a computer-simulated cooling towerI doubt that I could face the real thing.. In the meantime if you can bring me up to date on calcite and Ill start thinking again. TMLW, Oct. 1974

Calcite II [402 citations] Plummer, L.N., Wigley, T.M.L. and Parkhurst, D.L., 1978: The kinetics of calcite dissolution in CO2-water systems at 560C and 0.01.0 atm CO2. American Journal of Science 278, 179216.

Multiple simultaneous Reactions

CaCO3 + H2O (k3) CaCO3 + H+ (k1) CaCO3 + CO2aq (k2)

TML Wigley, 4 Nov., 1975

Microscopic Reversibility

TML Wigley, 6,7,8, Oct., 1975

Calcite II

A few more thoughts on CO2. The reason I was interested in a global map of the buffer factor, , was mainly to get a representative global mean . It is hard to keep up in this field, but it seems to me that there are some linked problems which a might solve. The calculated oceanic CO2 sink, which allows < 50% of the biological and fossil fuel CO2 to stay in the atmosphere, is too small. The sink strength is determined by . To find people use a global mean ocean chemistry and theoretical calculations or experiments (which both give different , but this is another problem). depends on chemistry in a non-linear manner. Thus, mean calculated from mean chemistry. Maybe the difference is enough to explain the problem of where all the CO2 is going?..... Sorry to go on about this, but it keeps coming back to me every time I see a new paper on global CO2--- and they are as thick as flies lately. To solve, even partly, the where is the CO2 going problem would be a plus. Im probably wrong, but it is an idea at least and I dont see that anyone has looked into it before Even if Im wrong, it would give an idea of how might vary with time. Small news item. I applied for the job of Director of C.R.U..
TMLW, 17 March, 1978

Wigley, T.M.L., 1976: Effect of mineral precipitation on isotopic composition and 14C dating of groundwater. Nature 263, 219221

Carbon mass balance

d ( mDIC ) dI i dOi
i 1 i 1 N M

Carbon-isotope mass balance

d ( RmDIC ) R dI i R i s dOi
* i 1 i 1 N M

Wigley, T.M.L., Plummer, L.N. and Pearson, F.J., 1978: Mass transfer and carbon isotope evolution in natural water systems. Geochimica et Cosmochimica Acta 42, 1117 1139.

Wigley, T.M.L., Plummer, L.N. and Pearson, F.J., 1979: ERRATA. Geochimica et Cosmochimica Acta 43, 1395.

Table 1 (p. 1120) was difficult to read and is reproduced below with equivalent expressions in terms of del values.

NETPATH: Net Geochemical Reactions along a Flow Path

DB
Database

WATEQF
Speciation
Tom Wigley

NETPATH
Mass Balance Electron Balance Isotope Balance Isotope Evolution Radiocarbon Dating

http://water.usgs.gov/software/netpath.html

Plummer, L.N., Prestemon, E.C., and Parkhurst, D.L., 1994, An interactive code (NETPATH) for modeling NET geochemical reactions along a flow PATH-- Version 2.0: U.S. Geological Survey Water-Resources Investigations Report 94-4169, 130 p.

At LGM, Atlantic Coastal Plain Recharge temps. 5-9oC cooler than Holocene. Lot of 20-30ka water preserved. Stable isotope enrichment in FL and south GA more than icevolume effect. Isotopic enrichment decreases northward.

The chronology is refined through application of the Wigley equations.

20

10 ka
N2 - Ar Recharge Temperature o Recharge Temperature, oC C
Local Shallow g.w. temp.

20 ka 30 ka

16

12
9 oC

4 0 5,000 10,000 15,000 20,000 Radiocarbon Age, Yrs 25,000

VIRGINIA