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Lateral thoughts on oxygen EUBS Amsterdam 2015
Mattijn Buwalda Anesthesiologist-intensivist Diving Medicine Physician
www.mattijnb.nl
Everything you always wanted to know about oxygen….
Content
and that was not in your textbooks
2
Light sky blue color of liquid oxygen
• Bohr model
• electron shells
• 2,8,18,32 electrons
• Oxygen has 6 electrons in outer shell
oxygen: physicochemical aspects
Oxidizer
• outer shell ‘needs’ 2 electrons
• oxidizer = electron acceptor
• reducer = electron donor 3
Covalent binding
4
1. most abundant chemical element on earth!
– 49.2% of the earth’s crust (by mass)
– 88.8% oceans (by mass)
2. second most abundant of the earth’s atmosphere
3. third most abundant in the universe
– after Hydrogen and Helium
– 0.9% of the Sun’s mass
– end product of Helium fusion in stars
Oxygen: hall of fame
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Wikipedia: oxygen lemma accessed may 2015
Earth’s atmosphere
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Life started without O2
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Miller & Urey 1950 Primordial soup hypothesis
http://www.abenteuer-universum.de/pdf/miller_1953.pdf Baross, J. A. & Hoffman, S. E. Submarine hydrothermal vents and associated gradient environments as sites for the origin and evolution of life. Orig. Life Evol. Biosph. 15, 327–345 (1985).
Hydrothermal vents: Emission of hot sea-water pH 2-11 Reacting with seabed rock Fe++/ Mn++/ H2/ CH4/ H2S /CO2 No sunlight or oxygen Autotrophic origin hypothesis: life started with CO2 & H2 Porous carbonate chimneys create • Ion gradient • pH gradient Chemi-osmotic coupling ATP production
early atmosphere: H2O, H2, NH3, CH4
Anaerobic energy
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Martin W, et al. Hydrothermal vents and the origin of life. Nature reviews microbiology. 2008;6:805-14
Anaerobic energy
Phototrophic proteobacteria
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Purple bacteria: Sunlight as energy source Reductor: (electron donor) • Fe++ • H2
• Sulfide or S (= purple sulfur bacteria)
Did not use H20 as electron donor Did not produce oxygen!
• H20 as the electron donor
• oxygen as a waste product!
The first photo synthesizers approx 3.8 billion yrs ago
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Cyanobacteria
• unicellular or colonial species
• planktonic cells
• biofilm in fresh water
• freshwater, oceans, bare rock
The first O2 producers
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Thylakoid membrane
proton gradient across the membrane powers ATP-ase O2 is a “waste” product
12
What about plants?
Mereschkowsky C (1905). "Über Natur und Ursprung der Chromatophoren im Pflanzenreiche". Biol Centralbl 25: 593–604.
• they came much later!
• 450 million yrs ago
• Chara globularis = pond weed
• evolved from the chlorophytes (colonized algae)
• closest relative to the first land plants
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Chloroplasts
14
Endosymbiosis 0.6-1.6 billion yrs ago
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Atmospheric oxygen
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1. First photosynthesizers, no O2 in atmosphere – O2 absorption by Fe in oceans – O2 absorption by land mass
2. slow build up 3. 4-5 % O2
4. the great oxygenation event 5. hyperoxic period (up to 35%)
21%
oxidation of dissolved iron to iron oxides: – Fe2O3 , FeO , Fe3O4
– precipitation layers in the ocean (iron ore)
– absorption on land surface
– 2 billion yrs ago: all the iron was oxidized and atmospheric O2 started to rise
Oxygen sinks
Fe2O3 hematite Fe3O4 magnetite 17
• mass oxidation of CH4 (strong greenhouse gas)
– producing CO2 (weak greenhouse gas)
– Huronian glaciation (2.4 to 2.1… billion yrs ago)
• extinction of most anaerobic organisms
– development of O2 based respiration
– more efficient ATP production
– evolution of multicellular and giant life forms during the ‘oxygen overshoot’ (300- 500 million years ago)
– average mammalian and reptilomorph fossil body size increased with the PO2 over last 65 million yrs.
The great oxygenation event 2.5 billion yrs ago
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Hyperoxic period
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Dino period
Gigantism
1995 Graham et al.: giant insects, millipedes, chelicerates occur during period of hyperoxic atmosphere
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Graham JB, et al. Implications of the later Palaeozoic oxygen pulse for physiology and evolution. Nature 1995;375:117-120
Arthropleura (milliped) reached 2 m (6 x length of present milipeds) Protodonata (Dragonfly)
now extinct
Harrison JF, et al. Atmospheric oxygen level and the evolution of insect body size. Proc R Soc B. 2010:277:1937-1946 Falkowski PG, et al. The rise of oxygen over the past 205 million years and the evolution of large placental mammals. Science 2005;309:2202-2204 VandenBrooks JM. The effects of varying partial pressure of oxygen on vertebrate development and evolution. 2007, PhD thesis, Yale university, New have, CT
Why are insects so small?
• no lungs or gills • diffusion driven oxygenation • small air ducts = tracheoles • diffusion distance limits body
size • tracheal diameter/ volume is
limiting factor 21
Darkling beetle
• developmental plasticity:
– hypoxia > smaller
– hyperoxia > bigger bugs with smaller tracheal system
– ∩ shaped response
22 Harrison, J. F, Kaiser, A. & VandenBrooks, J.M . Mysteries of oxygen and insect size. In 4th CPB Meeting in Africa: Mara 2008. Molecules to migration: the pressures of life (eds S. Morris & A. Vosloo) 2009, pp. 293-302. Bologna, Italy:M edimond Publishing.
Oxygen balance • bio matter and O2 have a 1:1 relation
– global photosynthesis vs global respiration – present day O2 production: 8.8 x 1015 mol/yr – production = consumption + carbon burial – burial of bio matter creates O2 excess – Earth’s atmosphere: 3.7 x 1019 mol O2
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https://uwaterloo.ca/wat-on-earth/news/earths-oxygen-revolution,
Atmospheric O2 variation
• hyperoxic period (300-500 million yrs ago)
– extension of swamp and lowlands
– excessive burial of swamp land (turf)
– development of land based plant life
– with degradation resistant lignin
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1) Electrolysis
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Electrolysis ISS US: OGS Ru: the elektron
2) Chemical
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1. electrolysis
2. chemical
3. pressure swing adsorption
4. fractional distillation air
Priestly & Scheele used:
• heating HgO & nitrates
• 2 HgO ==> 2 Hg + O2
• 2 KClO3 ==> 2 KCl + 3 O2
• 2 KMnO4 ==> K2MnO4 + MnO2 + O2
• needs activation
• “burns” at 600oC
• 15 minutes run time
• lithium perchlorate or sodium chlorate
• NaClO3 + Fe -> 3O2 + NaCl + FeO
Oxygen candle
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• zeolite filtration
• aluminosilicate
• 95% purity
3) Pressure swing adsorption
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home oxygen concentrators 5-10 L/m
Industrial Oxygen use
31
industrial O2 production
• 55% steel production
• 25% chemical industry
• 20% medical, welding and rocket fuel
4) Distillation
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N2 -196o C O2 -183o C Ar -186o C
the liquid with the lowest boiling point boils first! alcohol 78o C water 100
o C
Fractional distillation of air
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Linde Gas Schiedam NL
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• air intake: 50.000 M3/h
• O2 output: 10.000 M3/h
Air intake & filter
Linde Gas Schiedam NL
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molecular sieve air zeolite and silica gel adsorbents: • CO2
• Hydrocarbons • trace H20
Fractionation column
Linde Gas Schiedam NL
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Argon Column end product: LOX liquid oxygen
one grade only! medical & Industrial use
Oxygen storage
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Bag or flask J-sized cylinder (47.2L)
LOX
1 bar 137 bar 5 – 10 bar (up to 24)
volume x 1 volume x 137 volume x 842
LOX
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latent heat of vaporization maintains low temperature
usually pressurized to 5-10 bar
0.4 – 3% volume loss per day
Dewar open non-pressurized vessel
Air products safetygram 6: liquid oxygen
Latent heat of vaporization
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LOX-tank blowing of oxygen
Rise and fall of oxygen in medicine
The discovery phase
• Karl Scheele (Swedisch) – heating HgO & KNO3 – 1771 1777
• Joseph Priestly (English) – heating HgO – 1774, 1775 – removing phlogisticon
from air into HgO
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1778 Antoine Lavoisier (French) • named the gas: oxygène • the end of the phlogisticon theory
1783 …Caillens (French) • treated a young woman with phthisis
(TB) • daily oxygen inhalations
Priestly J. Observations on different kinds of air. Birmingham: Thomas Pearson 1775 OXYGEN GAS AS A REMEDY IN DISEASE, by Andrew H. Smith, M.D. New York: D. Appleton & Company, 1870
“From the greater strength and vivacity of the flame of a candle, in this
pure air, it may be conjectured, that it might be peculiarly salutary to the
lungs in certain morbid cases when the common air would not be sufficient
to carry off the putrid effluvium fast enough.
But, perhaps, we may also infer from these experiments, that though pure dephlogisticated air might be very useful as a medicine, it might not be so proper for us in the usual healthy state of the body; for, as a candle burns out much faster in dephlogisticated than in common air, so we might, as may be said, live out too fast, and the animal powers be too soon exhausted in this pure kind of air “
Priestly J. Observations on different kinds of air. Birmingham: Thomas Pearson 1775
A man with vision…..
Joseph Priestly
Pseudoscience period: a cure-all
• 1799 pneumatic institution:
– consumption, asthma, palsy, dropsy, venereal problems, scrofula and many other disease…
• Dr Birch 1869 lancet publication: oxygenated water and bread
Dr. Birch. Letter to the Lancet 1877;74:201
The origin of modern oxygen therapy
• Blodgett 1890:
– first documented continuous
(6 l/min) clinical use in pneumonia
• Adolph Fick (1829-1901)
– difference in arterial and venous oxygen pressure, cardiac output
• John Scott Haldane (1860-1936)
– 1917:the therapeutic administration of Oxygen
• innovative boost by WW I&II
• after WWII: general use of oxygen in clinical medicine
Blodgett AN. The continuous inhalation of oxygen in cases of pneumonia otherwise fatal, and in other diseases. Boston med Surg J 1890;123:481-4 Haldane JS. The therapeutic administration of Oxygen. BMJ 1917;i:181-3
The ‘hyperoxic’ period in medicine
Oxygen for every (sick) patient. protocolized (irrespective of sPO2)
More is not better……
American Academy of Pediatrics THE ROLE OF OXYGEN IN RETROLENTAL FIBROPLASIA E. Mead Johnson Award Address Pediatrics Vol. 19 No. 3 March 1, 1957 pp. 504 -524
The use of 100% O2 in anaesthesia • absorption atelectasis • respiratory depression in the PACU
THE PATHOLOGICAL EFFECTS DUE TO INCREASE OF OXYGEN TENSION IN THE AIR BREATHED. BY J. LORRAIN SMITH, M.A., M.D. The Journal of Physiology Volume 24, Issue 1, pages 19–35, March 22, 1899
COPD patiënts • increased V/Q mismatch • Haldane effect • resorption atelectasis • inhibition of hypoxic drive
Austin M a, Wills KE, Blizzard L, Walters EH, Wood-Baker R. Effect of high flow oxygen on mortality in chronic obstructive pulmonary disease patients in prehospital setting: randomised controlled trial. BMJ. 2010;341(oct18 2):c5462-c5462. Sassoon CH, Hassell KT, and CMahutte CK"Hyperoxic-Induced Hypercapnia in Stable Chronic Obstructive Pulmonary Disease", American Review of Respiratory Disease, Vol. 135, No. 4 (1987), pp. 907-911.
Myocardial infarction & CHF
The problem: (coronary) vasoconstriction during 100% O2
Beasley R, Aldington S, Weatherall M, Robinson G, McHaffle D. Oxygen therapy in myocardial infarction: an historical perspective. J R Soc Med 2007;100(3):130-133. Cabello JB. Et al. Oxygen therapy for acute myocardial infarction. Cochrane Database Syst Rev 2010;6:CD007160
• Cochrane analysis 2010: inconclusive
• 2004 American AHA guidelines: oxygen only if SaO2 < 90%
Post cardiac arrest
The problem: oxidative stress during reperfusion
• Meta-analysis of observational studies (50.000 patients) Wang et al. Resuscitation 2014;85:1142-48
• Retrospective analysis (n=184) Elmer J et al. Intensive Care Med 2015;41:49-57
2010 ERC guidelines recommend saturation 94-98%
more about oxygen….
ISBN-13: 978-1461258926 ISBN-13: 978-0691145020 ISBN-13: 9780198607830
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Thank you for listening! slides available @ www.mattijnb.nl
Salem Express Red Sea
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