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

5

Wikipedia: oxygen lemma accessed may 2015

Earth’s atmosphere

6

Life started without O2

7

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

8

Martin W, et al. Hydrothermal vents and the origin of life. Nature reviews microbiology. 2008;6:805-14

Anaerobic energy

Phototrophic proteobacteria

9

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

10

Cyanobacteria

• unicellular or colonial species

• planktonic cells

• biofilm in fresh water

• freshwater, oceans, bare rock

The first O2 producers

11

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

13

Chloroplasts

14

Endosymbiosis 0.6-1.6 billion yrs ago

15

Atmospheric oxygen

16

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

18

Hyperoxic period

19

Dino period

Gigantism

1995 Graham et al.: giant insects, millipedes, chelicerates occur during period of hyperoxic atmosphere

20

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

23

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

24

25

1) Electrolysis

26

Electrolysis ISS US: OGS Ru: the elektron

2) Chemical

27

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

28

• zeolite filtration

• aluminosilicate

• 95% purity

3) Pressure swing adsorption

30

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

32

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

33

Linde Gas Schiedam NL

34

• air intake: 50.000 M3/h

• O2 output: 10.000 M3/h

Air intake & filter

Linde Gas Schiedam NL

35

molecular sieve air zeolite and silica gel adsorbents: • CO2

• Hydrocarbons • trace H20

Fractionation column

Linde Gas Schiedam NL

36

Argon Column end product: LOX liquid oxygen

one grade only! medical & Industrial use

Oxygen storage

37

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

38

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

39

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

40

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

49

Thank you for listening! slides available @ www.mattijnb.nl

Salem Express Red Sea