An article was published in Nature Astronomy on 14th September, 2020, that reported the detection of a signal corresponding to the 1 – 0 rotational transition of phosphine, which has a wavelength of 1.123 mm. This was a very weak signal that had to be obtained by mathematical processing to remove artefacts such as spectral “ripple” that originate from reflections. Nevertheless, the data at the end is strongly suggestive that the line is real. Therefore they found phosphine, right? And since phosphine is made from anaerobes and emitted from marsh gas, they found life, right? Er, hold on. Let us consider this in more detail.
First, is the signal real? The analysis detected the HDO signal at 1.126 mm, which is known to be the 2 – 3 rotational transition. That strongly confirms their equipment and analysis was working properly for that species, so this additional signal is likely to be real. The levels of phosphine have been estimated as between 10 – 30 ppb. However, there is a problem because such spectral signals come from changes to the spin rate of molecules. All molecules can only spin at certain quantised energies, but there are a number of options, thus the phosphine was supposed to be from the first excited state to the ground. There are a very large number of possible states, and higher states are more common at higher temperatures. The Venusian atmosphere ranges from about 30 oC near the top to somewhere approaching 500 oC at the bottom. Also, collisions will change spin rates. Most of our data comes from our atmospheric pressure or lower pressures as doing microwave experiments in high-pressure vessels is not easy. The position of the lines depends on the moment of inertia, so different molecules have different energy levels, and there are different ways of spinning, tumbling, etc, for complicated molecules. Thus it is possible that the signal could be due to something else. However, the authors examined all the alternatives they could think of and only phosphine remained.
This paper rejected sulphur dioxide as a possibility because in the Venusian atmosphere it gets oxidised to sulphuric acid so there is not enough of it, but phosphine is actually far more easily oxidised. If we look at our atmosphere, there are actually a number of odd looking molecules caused by photochemistry. The Venusian atmosphere would also have photochemistry but since its atmosphere is so different from ours we cannot guess what that is at present. However, for me I think there is a good chance this signal is from a molecule generated photochemically. The reason is the signal is strongest at the equator and fades away at the poles, where the light intensity per unit area is lower. Note that if it were phosphine generated by life and was removed photochemically, you would get the opposite result.
Phosphine is a rather reactive material, and according to the Nature article models predict its lifetime at 80 km altitude as less than a thousand seconds due to photodegradation. They argue its life should be longer lower down because the UV light intensity is weaker, but they overlook chemical reactions. Amongst other things, concentrated sulphuric acid would react instantaneously with it to make a phosphonium salt, and while the phosphine is not initially destroyed, its ability to make this signal is.
Why does this suggest life? Calculations with some fairly generous lifetimes suggest a minimum of about million molecules have to be made every second on every square centimeter of the planet. There is no known chemistry that can do that. Thus life is proposed on the basis of, “What else could it be?” which is a potential logic fallacy in the making, namely concluding from ignorance. On earth anaerobes make phosphine and it comes out as “marsh gas”, where it promptly reacts with oxygen in the air. This is actually rather rare, and is almost certainly an accident caused by phosphate particles being in the wrong place in the enzyme system. I have been around many swamps and never smelt phosphine. What anaerobes do is take oxidised material and reduce them, taking energy and some carbon and oxygen, and spit out as waste highly reduced compounds, such as methane. There is a rather low probability they will take sulphates and make hydrogen sulphide and phosphine from phosphates. The problem I have is the Venusian atmosphere is full of concentrated sulphuric acid clouds, and enzymes would not work, or last, in that environment. If the life forms were above the sulphuric acid clouds, they would also be above the phosphoric acid, so where would they get their phosphorus? Further, all life needs phosphate: it is the only functional group that has the requirement to link reproductive entities (two to link a polymer, and one to provide the ionic group to solubilize the whole and let the strands separate while reproducing), it is the basis of adenosine tripolyphosphate which is the energy transfer agent for lfe, and the adenosine phosphates are essential solubilizing agents for many enzyme cofactors, in short, no phosphate, no life. Phosphate occurs in rocks so it will be very scarce in the atmosphere, so why would it waste what little that was there to make phosphine?To summarize, I have no idea what caused this signal and I don’t think anyone else has either. I think there is a lot of chemistry associated with the Venusian atmosphere we do not understand, but I think this will be resolved sooner or later, as it has got so much attention.