Why does the oxygen produced in the photosynthesis come from water and not carbon dioxide?

Question

In the photosynthesis equation:

$$\ce{6CO2 + 6H2O ->[sunlight] C6H12O6 + 6O2}$$

The only place where we have 6 molecules of $\ce{O2}$ is in $\ce{6CO2}$. Then it reacts with $\ce{6H2O}$ to form $\ce{C6H12O6}$ and $\ce{6O2}$ that apparently comes from $\ce{CO2}$. So why do we say that the $\ce{O2}$ produced by plants comes from $\ce{H2O}$ and not $\ce{CO2}$? I don't know if I'm the one who's understanding something wrong or is it the photosynthesis formula which is wrong?

Answer 1

You are missing some knowledge here for sure, photosynthesis is a little complicated at A level, so I will describe it in brief.

During photosynthesis electrons and protons (A hydrogen atom without the electron) are required for a process called the electron transport chain and proton motive force. This happens during the light dependent stage of photosynthesis, (there is also a second light-independent stage called the Calvin cycle, and that is where the CO$_2$ is used), I won't go into detail about what the protons and electrons do (unless you want me to) but you need to know that these come from a water molecule, the water is split using light (photolysis, literally: cutting with light) into two hydrogens and half an oxygen molecule (or an oxygen atom). The oxygen that was released in photolysis is not required for the rest of the pathway, so it diffuses out of the cell.

For why it doesn't come from carbon dioxide, you need to consider the Calvin cycle. In the Calvin cycle, carbon dioxide is converted to glucose by enzymes, using products from the light dependent stage, so 6CO$_2$ are combined over six cycles to form one molecule of glucose. So that is where the CO$_2$ is used as well.

Hope that helped! If you want me to go into any more detail please ask!

Answer 2

Photosynthesis uses chlorophyll (or other pigments) for harnessing photons and water (or other compounds) as electron donor $H_2O = 1/2O_2 + 2H^+ + 2e^-$. After splitting the water it sends the electrons through the further steps of an electron transport chain and at the end it reduces $NADP^+$ into $NADPH$. Meanwhile it increases the $H^+$ concentration outside of a membrane, so it creates a $H^+$ gradient. This gradient can be used to synthesize $ATP$ from $ADP$ using a $H^+$ pump. After that $NADPH$ and $ATP$ can be used to fix $CO_2$ at any time (so that part of the photosynthesis is not light dependent).

• Figure 1 - Light-dependent reactions of photosynthesis - electron transport chain - source

Splitting $CO_2$ into $CO$ and $1/2O2$ is possible as well. It can be done enzymatically or due to photolysis. You need similar energy to do that as by water splitting. After that $CO$ can be used e.g. by shift reaction $CO + H_2O = CO_2 + H_2$ to create an electron donor ($H_2$) and play the same thing as normally. It is possible to reduce $CO$ with an electron donor ($_H2O$, $H_2$, $H_2S$, $NH_3$, etc...) further, and create for example ethanol or carbohydrates like glucose.

Afaik only artificial photosynthesis use $CO_2$ splitting and natural ones prefer $NADPH$ and $ATP$ creation and usage for example in the Calvin cycle, C4 pathway, CAM pathway, reverse Krebs cycle, Wood pathway, etc... I think this is because carbon fixation evolved before photosynthesis. So photosynthesis is just about plugging another energy source into the system.

(In programmer terms the carbon fixation is loosely coupled to the implementation of the energy producing process and the common interface is described with ATP and NADPH creation. In mobile phone user terms it is like charging your phone's battery (ATP and NADPH storage) from line power or using a solar charger. Both chargers provide electricity (ATP and NADPH) via USB.)

The question is good, what you meant is possible, but afaik. in natural photosynthesis the $O_2$ always comes from the water.

References:

• 2006 - Photosynthesis in the Archean era.
• 2008 - When did oxygenic photosynthesis evolve?
• 2012 - On the photosynthetic potential in the very Early Archean oceans
• 2010 - Early Evolution of Photosynthesis
• 1988 - Photoreduction of carbon dioxide by aqueous ferrous ion: An alternative to the strongly reducing atmosphere for the chemical origin of life
• wikipedia - Anoxygenic photosynthesis
• 2002 - Kinetic study of the reverse water gas shift reaction in high-temperature, high-pressure homogeneous systems
• The Enthalpy, Entropy and Gibbs Energy of Ion Formation in Solutions
• wikipedia - Standard enthalpy of formation
• 2012 - Splitting CO2 into CO and O2 by a single catalyst
• 2002 - Molecular Hydrogen as an Energy Source for Helicobacter pylori
• 2009 - Water-Gas Shift Reaction Catalyzed by Redox Enzymes on Conducting Graphite Platelets
• 2013 - Leaf-architectured 3D Hierarchical Artificial Photosynthetic System of Perovskite Titanates Towards CO2 Photoreduction Into Hydrocarbon Fuels
• 2014 - Comparison of CO2 Photoreduction Systems: A Review
• 2006 - Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction
• 1972 - Flash photolysis of H2S
• 2011 - Anoxygenic Photosynthesis
• 2004 - Time line of discoveries: anoxygenic bacterial photosynthesis
• 1990 - A reverse KREBS cycle in photosynthesis: consensus at last
• 2009 - Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels
• 2014 - Electroreduction of carbon monoxide to liquid fuel on oxide-derived nanocrystalline copper
• 2012 - Biological conversion of carbon monoxide to ethanol: effect of pH, gas pressure, reducing agent and yeast extract.
• 2012 - Hydrogen, metals, bifurcating electrons, and proton gradients: The early evolution of biological energy conservation - an exciting article
• 2005 - Hydrogen-driven subsurface lithoautotrophic microbial ecosystems (SLiMEs): do they exist and why should we care?
• 2011 - Alternative Pathways of Carbon Dioxide Fixation: Insights into the Early Evolution of Life?
• 1998 - Hydrogen metabolism in organisms with oxygenic photosynthesis: hydrogenases as important regulatory devices for a proper redox poising?
• 1975 - Facultative anoxygenic photosynthesis in the cyanobacterium Oscillatoria limnetica.
• 2003 - On the origins of cells: a hypothesis for the evolutionary transitions from abiotic geochemistry to chemoautotrophic prokaryotes, and from prokaryotes to nucleated cells
• 2011 - Serpentinite and the dawn of life
• 2010 - How did LUCA make a living? Chemiosmosis in the origin of life
• 2012 - The Emergence and Early Evolution of Biological Carbon-Fixation
• 2012 - Photosynthetic Electron Transport in an Anoxygenic Photosynthetic Bacterium Afifella (Rhodopseudomonas) marina Measured Using PAM Fluorometry
• Bacterial Energetics: A Treatise on Structure and Function
• 2012 - Depth variation of carbon and oxygen isotopes of calcites in Archean altered upperoceanic crust: Implications for the CO2 flux from ocean to oceanic crust in the Archean
• 2013 - Hydrogen-Nitrogen Greenhouse Warming in Earth's Early Atmosphere
• 2010 - Aeronomical evidence for higher CO2 levels during Earth’s Hadean epoch
• 2014 - From Ionizing Radiation to Photosynthesis
• 2011 - Metal centers in the anaerobic microbial metabolism of CO and CO2
• 2014 - Evidence and arguments for methane and ammonia in Earth's earliest atmosphere and an organic compound–rich early ocean

Answer 3

It’s not about the oxygen!

This question indicates two misplaced concerns. One is with oxygen. I imagine that this is because of its importance to us as animals; however as far as photosynthesis is concerned oxygen is just a waste product. The other is with a chemical equation, which is as informative as the top line of a commercial balance sheet. One's focus should be on the chemical problem and what is needed to solve it.

The problem is making sugar from carbon dioxide

The purpose of photosynthesis is to make sugar from carbon dioxide. Why is this a problem?

• The individual carbons in the carbon dioxide have to be joined together with C-C bonds. This requires energy (in the biological form of ATP).
• In sugars most of the oxygen atoms are in OH groups. So we need to convert the C=O of the carbon dioxide to C–OH (not throw the oxygen away). This is reduction of the carbon, and requires ‘reducing power’ (in the form of the NADPH) which also requires energy input.

The sun solves the problem by supplying the energy

The energy for creating the reducing NADPH and the ATP comes from the sun in a complex series of reactions that do not involve carbon dioxide. Light of a particular wavelength is used to break a water bond so as to separate charge in a reaction that I will deliberately not balance:

(1) H₂O → O₂ + H

A complex series of reactions transfer the H (more strictly an electron) between different molecules, eventually reducing NADP⁺ to NADPH. At the same time an equally complex process builds up a H⁺ concentration difference across a membrane which provides the energy to convert ADP to ATP.

To reiterate, the reaction uses light energy to generate chemical energy in the form of NADPH and ATP. Oxygen is just flushed down the toilet.

Now for the Lego bricks — so easy we can do it in the dark

Having harvested the energy of the sun we have money in the bank which we can spend whenever we want — day or night — to make sugar from carbon dioxide. The overall unbalanced equation is:

(2) CO₂ + NADPH + ATP → C₆H₁₂O₆ + NADP⁺ + ADP

but this is actually a complex series of enzyme-catalysed reactions (known as the Calvin Cycle if you must know).

You still want to know the answer?

The oxygen produced in photosynthesis comes from water because this is the molecule in which a bond is broken by sunlight to separate charge allowing synthesis of molecules with reducing power and energy transfer potential. Carbon dioxide is the building block of the sugar and far from breaking a C=O bond, what is needed is for it to be converted to C-OH by reduction of the carbon.

Answer 4

I read on Wikipedia that basically 3 $O_2$'s come from water in the light reaction, and during the Calvin cycle $H_2O$ is produced from H+ ions and $CO_2$ to make more $H_2O$, which produces more $O_2$ in the light reaction.

Basically, 3 $O_2$'s come from the water and the other 3 $O_2$'s come from $CO_2$-made $H_2O$.

EDIT: The equation is $12H_2O$ + $6CO_2$ => $C_6H_1$$_2$$O_6$ + $6H_2O$ + $6O_2$ so therefore all the $O_2$ is from the water, and the $O_2$ in the sugar is from the $CO_2$, and the supposedly extra $O_2$ left over goes into some new $H_2O$.