180 Years of atmospheric CO2 Gas Analysis by Chemical Methods – Support

180 Years of atmospheric CO2 Gas Analysis by Chemical Methods – Support

StD Ernst-Georg Beck, Dipl. Biol. 2006/2007
email: egbeck@biokurs.de

Merian-Schule Freiburg; Dep. Biotechnology and Nutrition Science
79104 Freiburg, Rheinstr. 3, Germany


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180 Years of atmospheric CO 2 Gas Analysis by Chemical Methods


7 essential points of my paper in pictures, English Summary
German summary scientific
German summary normal

Part 4 of projected monograph “History of CO 2 Gas Analysis of Air by Chemical Methods”

uncorrected, unfinished, not authorized for publication, only for evaluation

Basic database (>90 000 series, 143 averages over 150 years, >53 locations ) 8-006
Bibliographies historic measurements

Letts&Blake 19th century, table of known measurements
Letts&Blake 19th century bibliography (252 papers)

Effenberger 1951 table of measurements
Stepanova (1952) 20th century (99 papers) Bibliography of Abstracts,
Historic papers (CO2 peak 1942) Data – Methods
Van Slyke (1933) – 1932 I, II, III
Haldane (1936) Scotland ~ 350 ppm
Duerst (1936-1939) 400 ppm (*.doc)
W. Kreutz: Gießen 1939-41>420ppm (German); English A. Bijkerk
W. Kreutz 1939 Spezialinstrumente… (weather station Giessen)
Riedel C Kohlensäurebest.apparat (Schuftan) (*.doc), Gasanalyser Kreutz
Official Map of Giessen 1939
Weather Station at Giessen with possible anthropogenic sources
Mining activities in Hessen -1940: total map, map east, map west
Bazett (1941) 400 ppm Philadelphia
MIsra (1941-1943) (*.doc) >400 ppm in India
Lockhart (1941-1942) >600 ppm in Antarctica
Hock et al. (1947-1949) 400 ppm Point Barrow
Fonselius (1955) Method, Fonselius 1955 -59 ( Scand. network) 323 ppm
Steinhauser 1957/58, Wien 325ppm
Historic Papers CO2: 1900 – 1927, Data – Methods
Brown&Escombe 1898-1901; Kew Garden UK 294 ppm
Otto Warburgs Gasanalyser, improved Pettenkofer 1909 I, II, III, IV
F.G. Benedict, The Composition of the Atmosphere (book too large, 115p) p74-115; 1912
A. Krogh 1919. The Composition of the Atmosphere 305 ppm
J.S. Haldane “Methods of Air Analysis”, 1920; 137p; too large; content
H. Lundegardh CO2 -1920-1926 part I,part II ~310 ppm
Historic Papers CO2: 19th Century, Data – Methods
C.E. Brunner , Journ. de Pharm, 18, 1832; drying air with H2SO4
C.E. Brunner ” Annales de chimie et de physique 1841 (3e série / Tome 3). P. 305, Gasanalyser end of journal; drying air by H2SO4 p312

H. Hlasiwetz (1856) ” Über Kohlensäurebestimmungen der atmosphärischen Luft”
H2SO4 absorbs CO2: p.193 ; discussion of erroneous methods

v. Gilm (1857) Innsbruck: Über die Kohlensäurebestimmung der atm. Luft 383 ppm

Schulze (1864) Rostock: On the amount of carbonic acid in air… 360 ppm
Schulze (1868-71) Rostock: Daily Observations on the… 292 ppm

Regnault 1871 drying air by H2SO4

Annales de chimie et de physique, 1871 (4e série / Tome 24). p.257-258
Haesselbarth/Fittbogen 1874/75 Dahme (Prussia) 334 ppm
Farsky (1874/75) Tabor, Cz 343 ppm
Reiset (1879) “Recherches sur la proportion de l´acide carbonique dans l´ air” ~293 ppm
Armstrong (1879) summer/autumn Grasmere UK 313 ppm (day/night)
Reiset (1882) “Recherches sur la proportion de l´acide carbonique dans l´ air”
Hempel (1884) Winter, City of Dresden 375 ppm
Spring (1883) Liege (B) 335 ppm ; p45-91, critics drying air by H2SO4 p.65-69; data
Uffelmann (1886) Rostock; city: 351 ppm, outside: 318 ppm
Petermann (1889-91) Gembloux (Belgium) 294 ppm
Letts&Blake (1897) Belfast
Evaluation of historic papers on CO2: Callendar – Keeling etc.

Callendar (1958) “On the amount of CO2 in the Atmosphere”

See Callendars rejection of inaccurate values concerning free air p. 244 a) and d):

CO2 values are inaccurate when: ” period mean values 10% or more different from general average of time and region” or

“by measurements intended for special purpose such as biological, soil air, atmospheric pollution etc.”

Callendar (1940) “Variations of the Amount of Carbon Dioxide in Different Air Currents” (*.doc)
Keeling 1978 (Atmosph. CO2 in 19th century)
Wigley 1983 The Preindustrial Carbon Dioxide Level
WMO Meeting ” CO2 concentrations from pre-industrial times to I.G.Y 1983
EOS meeting 1984

Keeling: 1986 Reassessment of late 19th Century atmospheric carbon dioxide variations…..(zip)

See Keelings discussion of low values of Reiset and Muentz p. 88

Keeling p 91: “Muentz & Aubin rivaled Reiset at professing to be among the most careful of the 19th century investigators of CO2” He had not investigated many others!

Keeling p. 103: “…Reiset…and his results show no abnormally low concentrations suggestive of incomplete absorption.” Wrong: He used H2SO4 for drying the air before absorption, and H2SO4 absorbs a considerable fraction of CO2, so his values are systematicly too low. Keeling was chemist! ( See Reisets article of 1880: Compt. Rend. 90, 1880, p. 1145) above.

Keeling Speech 1993, Winner second blue Planet Prize
Keeling citation on historic gas measurement

Historic Gasanalyzers – Methods

Pettenkofer 1858: method determining carbonic acid in air

Pettenkofers Respirationsapparat 1866

Tissandier 1875
46 Historic Respiration Apparatures 1876-1928
Muentz&Aubin 1882
H. Lundegardh ( 1922) New apparatus to analyse CO2 content in air
A. Krogh 1920 ; Krogh 1929 (Methode Fonselius 1955-)
Van Slyke Gasanalyser 1932
Riedel C Kohlensäurebest.apparat (Schuftan) (*.doc) 1933
P.F. Scholander Gasanalyser 1947; Gasanalyser 1984
Thomas (1933) Automatic Gasanlyser (zip)
Pettenkofer process and its variants
Pettenkofer 1858: method determining carbonic acid in air (original, german)
Schulze 1868-71 (german)
Hesse “Determination of carbonic acid in air” (1877) (german)
Armstrong summer/autumn Grasmere UK (1879)(english)
Uffelmann 1886 (german)
Petermann 1889 (french)
Brown&Escombe 1900 (english)
Technology of gas analysis (P. Schuftan 1931) (german)
Kauko (1935) “Accurate determination of CO2 in air ” (german)

Kauko 1934 Description of Pettenkofer variants (german)

Description of Pettenkofer process in Abderhalden, Handbook of biochemical methods 1920
Description of Pettenkofer process in Treadwell (Textbook of anal. chemistry 1949) in english
Advantages of Butyl Rubber in Organic Analysis 1948

Biographies of famous scientists involved in CO2 gas analysis

Thénard, Louis J., 1777-1857 French chemist , wrote first textbook of chemistry
NICOLAS THÉODORE DE SAUSSURE: 1767 –1845 swiss chemist, founder of plant physiology

Henri Victor Regnault 1810 –1878, French chemist and physicist,Thermodynamics

Max v. Pettenkofer (1818-1901 ) German physician founder of hygiene
J.A. Uffelmann ( ) german physician, hygiene
Benedict, F. G. (1870-1957 ) Pinoneer in nutrition science
August Krogh (Nobel Award 1923) 1874-1949
J.S.Haldane 1860-1636 British physiologist, pionieer of O2 therapy
Henrik Lundegardh (1912 – 1969 ) pioneer in plant physiology
Paul Schuftan, (1896-1980) German chemist, Pionieer of Gaschromatography
D.D. van Slyke ( ); 1883 –1971, US chemist , pioneer in blood gas measurement and more
Per F. Scholander (1905-1980 ), Swedish physician and physiologist, pioneer in blood gas measurement
Modern measurements
CO2 flux Scots pine forest..s. Germany , 30 m 2003 (408 ppm) Diurnal: 380 – 460ppm
CO2 Cub Hill (USA) 2001
Evaluation of CO2 flux , Forest at Dresden 1996-2001
C13/C12 reconstruction from tree-rings 1979, past CO2 levels
C13/C12 reconstruction from tree-rings 1982
200 years Temperature, Antarctica Ice Core (Schneider et al. 2006)
Compiled data of historic measurements – EXCEL
Saussure 1830, vGilm 1857, Schulze 1864, Schulze 1871, Farsky 1874, Hasselbarth 1875, Reiset 1872-1879, Muentz 1881, Spring 1883: I + II, Uffelmann 1887, Petermann 1889, Letts&Blake 1897, Brown&Escombe 1898-1901, Benedict 1909-12, Lundegardh 1920-26, Buch 1932-35,Duerst 1936, Kreutz 1939-41, Misra 1942/43, Scholander 1946, Steinhauser 1957 ,
Background approximation: Kreutz(1939), Steinhauser (1957) , Diekirch_Lux(2005)
CO2 -1857, CO2-1857-1880, CO2-1880-1927, CO2-1942-spike , 1800-2004 (5)
oxygen deficiency 19th century (~1857)
moon cycle: Mauna Loa 2004, Diekirch [Lux]2005,
Historic chemical data fit with modern ice core records (Antarctica)
-Schneider et al. 2006 – Beck 2007-
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