In the long and intermittently very interesting comments thread to the previous post, there's some more discussion of what we should think about formaldehyde. Formaldehyde is one of the trace chemicals that Vittorio Formisano talked about looking for using the Mars Express PFS in his interview with Linda Moulton Howe. And while Formisano does not claim to have detected formaldehyde, such a claim was made a decade ago by scientists using an instrument called Auguste on the 1989 Soviet Phobos mission (Korablev, O.I., Ackerman, M., Krasnopolsky, V.A., et al., Tentative Identification of Formaldehyde in the Martian Atmosphere, Planetary and Space Science vol. 41, pp. 441-451.)
Since formaldehyde is an organic chemical that could most easily be made out of methane, you'd think that the discovery of formaldehyde on Mars would be a big thing, since it would imply the existence of methane. (Though there are other ways to make formaldehyde on Mars, they probably wouldn't make a lot, and they'd be local to the ice caps). The reason the 1993 formaldehyde paper is not seen as a big thing is that, by and large, I don't think anyone -- including the people who made it -- really puts much faith in it these days.
That's not to say no-one talks about it. As Rick Sterling points out in those previous comments, the tentative detection made in 1993 is cited in a 2003 paper by Formisano and colleagues entitled "Atmospheric Photochemistry Above Possible Martian Hot Spots", (a paper presented at COSPAR, I think, not one published in a journal). This paper asks what an instrument like the Mars Express PFS might expect to see if there's a little volcanism still going on on Mars. The authors say that one explanation for the formaldehyde might be a "large flux of methane from a localized source in the Martian atmosphere" such as a volcanic hotspot. Rick also points out a 1999 paper (Weiss B, Yung, Y & Nealson K, Atmospheric Energy For Subsurface Life On Mars, PNAS, vol 97, pp1395-1399) where the authors say "Formaldehyde, which has no known geological source on Mars & has a lifetime in the Martian atmosphere of only 13 hours, may have already been detected by the Phobos spacecraft, although this is uncertain". On the issue of uncertainty the paper references a 1997 paper by Krasnopolsky, Mumma and colleagues in which formaldehyde was not detected in earth-based measurements at anything like the level apparently seen from the Phobos spacecraft (Krasnopolsky, V., Bjoraker, G., Mumma, M. & Jennings, D. J. Geophys. Res. vol 102, pp6525–6534).
To me, though, the key is a 2002 paper in which the first author on the original formaldehyde detection paper provides a detailed summary of the Auguste instrument's measurements (Korablev, O. I., Solar Occultation Measurements of the Martian Atmosphere on the Phobos Spacecraft: Water Vapor Profile, Aerosol Parameters, and Other Results, Solar System Research vol 36, pp12-34). It's a paper written largely from a desire to dispel the idea that the Phobos mission was an ignominious failure; as Korablev argues, it sent back more useful data than all the USSR's previous Mars missions combined (though that's not as grand an achievement as it might sound). To make this case Korablev goes through the relevant data very carefully, seeking to provide a definitive account of the achievements.
In his discussion of the features in the 3.7 micron region of the infrared spectrum that he and his colleagues had tentatively described as absorption by formaldehyde, Korablev shows that in the final analysis, if you explain the data from the relevant two pixels (yes, just two) of the spectrum by invoking formaldehyde, you get a formaldehyde level of between 200 and 1,300 parts per billion, with a best estimate of 500 parts per billion. That's slightly lower than the figure they originally published -- but still a staggering fifty times the level currently being quoted for methane. And Korablev himself does not believe it.
He goes on to compare this interpretation of the data to ground based observations -- some published, some not -- including those of his co-author on the original paper, Krasnopolsky (who, in case anyone has forgotten, leads one of the teams that reported methane earlier this year). Those observations, which have much better spectral resolution, set limits on the formaldehyde level of 3 parts per billion or less. That's a two or three order of magnitude difference between what the spacecraft seems to be saying and what the earthly observers say. What's more, it's very hard to imagine what might be producing formaldehyde in the huge amounts implied by the Phobos data, since methane levels are so much lower; if formaldehyde is being made from methane, which has a longer atmospheric life, you'd expect there to be a lot less of it, not a lot more. (As I read it, the Formisano et al “Hotspots” paper mentioned above calculates that formaldehyde should be about ten million times less common than methane if it’s being made from methane in the atmosphere). Nor does Korablev think the formaldehyde hypothesis can be saved by suggesting that it's a very local phenomenon related to a hotspot or a life-bearing oasis. The relevant spectra were measured over completely different locations on Mars.
On the basis of all this, Korablev concludes that the features seen by Auguste in the 3.7 micron region cannot have been due to formaldehyde. And I conclude, yet again, that making sense of spectra is a very tough and time-consuming affair.
In their 2003 paper "Atmospheric Photochemistry Above Possible Martian Hotspots" Formisano,Etc. state,"A tentative detection of 0.5 PPM of formaldhyde(CH20)in the equatorial region in the northern spring(Korablev et al 1993)if confirmed, could, however,imply a large flux of Methane from a localized source in the Martian atmosphere. With the above in mind & due to the considerable interest in the question of extinct or extant life on Mars, we have developed a one-dimensional model, considering the possibility that CH4, SO2 & H2S may be introduced into the Martian atmosphere". Later the research paper states, "Thus the best candidates of chemical markers of any hotspots on Mars are SO2, H2S, CH4, possibly SO,CH2O CH3OH. The largest source of methane in the earth's atmosphere is methanogenic bacteria living in anaerobic soils in tropical forrests, swamps & rice paddies & in the guts of cattle & other grass eating animals wirh smaller contributions from fossilized matter. Methane & it's products could serve as possible biomarkers in the Martian Atmosphere as well. Thus Formisano,etc.see a possible,definite conection between the discovery methane,formadehyde,etc and Martian life. Finally ESA stated in its article "Mars Express Confirms Methane in the Martian Atmosphere"(March 30,2004), "One of the aims of the mission is analysing in detail the chemical composition of the Martian atmosphere, known to consist of 95% percent carbon dioxide plus 5% of minor constituents. It is also from these minor constituents, which scientists expect to be oxygen, water, carbon monoxide, formaldehyde and methane, that we may get important information on the evolution of the planet and possible implications for the presence of past or present life. The URL for the ESA Mars methane confirmation article is http://www.esa.int/SPECIALS/Mars_Express/SEMZ0B57ESD_0.html
Posted by: Rick Sterling | August 16, 2004 at 04:01 PM
Nice post, Oliver. I dug out the 2002 Korablev paper from my personal collection of Solar System Research reprints. Not only does he report a lack of confidence in his earlier (1993) paper, he referenced unpublished results from Marten et al. (1995), which utilized IRAM millimeter-range radio spectroscopic data. Marten et al. constrained formaldehyde (CH2O) concentrations to a maximum of 0.11 ppb. Moreover, he notes the longer lifetime (on the order of years) of methane (CH4) in the Martian atmosphere would result in its more even distribution. He concludes that trying to explain (apparent) local enhancements of formaldehyde as a result of photochemistry from a more uniformly mixed methane distribution is, at the very least, implausible.
Posted by: Alex R. Blackwell | August 16, 2004 at 06:44 PM
Here is the URL to Richard Hoagland's(The Enterprise Mission) new article about V. Formisano's Formaldehyde & HS research. Very interesting article! http://www.enterprisemission.com/FormisanosTwilightZonePart2.htm
Posted by: Rick Sterling | August 20, 2004 at 12:39 PM
For those who feel grubby simply reading Hoagwash the article shows that the title of a presentation to be given by Formisano on 20 Sept at the ASI International Mars conference was changed sometime between 5th and 12th August from
"PFS Observation of methane Formaldehyde and HS: Extant Life on Mars?"
to
"the resultats [sic] of the PFS instrument"
Note no mention of Ammonia in either, but that second clause in the original title is pure dynamite!
That prompted me to re-read the Nature denial of ammonia. In that article Formisano has clearly communicated no Ammonia but the only direct quote is
"They want to shoot first, and they shoot the wrong statement"
I think Formisano is using "shoot first" in the sense of "shoot first ask questions later", but what is interesting is the second part of the quote. He says they shoot (sic) the wrong statement implying there was/is a right statement they could have shot.
I then re-read the earthfiles interview in which Formisano makes clear he is speculating on premliniary data and was in the process (in May) of digesting far better data and was hoping to make an announcement in September.
I'm not a scientist so don't have to worry about going out on a limb. All of the above suggests to me the following speculative chain of events
Feb - Tentative detections of a slew of bio-marker molecules including but not limited to Methane, Ammonia, Formaldehyde & Benzene
April - Earthfiles interview & new better data coming in, also submission of COSPAR abstact.
May/June - New stronger data processed and PFS team realise the Ammonia signal can not be stood up, but that Formaldehyde and HS can be.
June/July - Submit speech title for ASI conference which Formisano has earlier indicated is his prefered venue for going public (he is Italian after all!)
July - BBC article sends ESA & PFS team into a flat spin
August - Someone amends ASI speech title to avoid another BBC type fiasco
September - Formisano gets to make his big announcement on "Extant life on Mars?"
Posted by: blairf | August 20, 2004 at 11:47 PM
The Enterprise Mission(RCH) has now updated their article on the Sept,2004 Italian Mars Conference to include a link to the originial version of The Italian Mars Conference pdf file. http://www.enterprisemission.com/FormisanosTwilightZonePart2.htm
Posted by: Rick Sterling | August 21, 2004 at 09:35 PM
The Italian Mars Conference at Ischia Island will announce tomorrow that the Mars Express PFS has found Methane, Formaldehyde & HS on Mars. It's Third Announcement statment was recently changed to include this information. V. Formisano will present this extremely important data at that time. These gases are very strong indicators of life on Mars. The URL for the Ischia Mars Conference is http://www.asi.it/html/ita/news/Ischia1.pdf
Posted by: Rick L. Sterling | September 20, 2004 at 12:18 AM
Water and methane maps overlap on Mars: a new clue?
20 September 2004
ESA PR 51-2004
http://www.esa.int/export/SPECIALS/Mars_Express/SEML131XDYD_0.html
Posted by: Alex R. Blackwell | September 20, 2004 at 05:16 PM
Mars Express Yields Provocative Observations
By Leonard David
Senior Space Writer
posted: 20 September 2004
02:12 pm ET
http://www.space.com/scienceastronomy/express_methane_040920.html
Posted by: Alex R. Blackwell | September 20, 2004 at 07:20 PM
New Mars data gives life clue
BBC News
Last Updated: Monday, 20 September, 2004, 15:47 GMT 16:47 UK
http://news.bbc.co.uk/2/hi/science/nature/3673248.stm
Posted by: Alex R. Blackwell | September 20, 2004 at 10:00 PM
Published online today in the Early Edition of the Proceedings of
the National Academy of Sciences:
Henry P. Scott, Russell J. Hemley, Ho-kwang Mao, Dudley R.
Herschbach, Laurence E. Fried, W. Michael Howard, and Sorin Bastea
Generation of methane in the Earth's mantle: In situ high pressure-
temperature measurements of carbonate reduction
PNAS published September 20, 2004, 10.1073/pnas.0405930101 (Geology)
PDF http://www.pnas.org/cgi/reprint/0405930101v1
Posted by: Alex R. Blackwell | September 20, 2004 at 11:02 PM
That's an interesting paper, Alex -- thanks for the link. It's worth keeping in mind that the source of the methane they discuss is, if I understand correctly, subducted carbonate, so to do the same on Mats would require both subduction and carbonates. There's some carbonate on Mars (at least there's some in the martian meteorites), but not all that much, as far as we know, and there's no known mechanism for subducting it down into the mantle.
Posted by: Oliver Morton | September 21, 2004 at 12:24 AM
From the ESA press release: "The PFS instrument has also detected traces of other gases in the Martian atmosphere. A report on these is currently under peer review. Further studies will address whether these gases can be linked to water and methane and help answer the unresolved questions."
The kicker, if confirmed, would be formaldehyde -- I gather that there is probably no workable nonbiological explanation for that, whereas (as Oliver keeps pointing out) methane and hydrogen sulfide could have volcanic origins. (Given the UV-stimulated atmospheric chemistry of Mars, though -- and the fact that its air has lots of carbon -- are we SURE that there is no possible non-biological formation mechanism for formaldehyde?)
Posted by: Bruce Moomaw | September 21, 2004 at 02:23 AM
The Enterprise Mission has published a copy of the abstact V. Formisano presented at the Ischia Mars Conference. Formisano states in his abstract that the Mars Express PFS found Formaldehyde on Mars.The URL for the Enterprise Mission article is http://www.enterprisemission.com/formisanosAbstract.php
Posted by: Rick L. Sterling | September 21, 2004 at 06:40 AM
Thanks for sharing the Formisano and Cottini abstract, Rick. It is intriguing and the PFS data certainly deserve follow up, though, more importantly, they also deserve the strictest scrutiny.
That said, however, the title of the TEM web page you linked to, "Formisano Publishes Ischia Conference Data Indicating 'Current Life on Mars' ... but Wimps Out in Live Presentation!," contains, not surprisingly, at least two outright misstatements.
First of all, Formisano and Cottini qualify the portion of the abstract title "[Extant] Life on Mars" with a "?", indicating the preliminary nature of their data and the speculative nature of the implications of their observations. One should note that at no point do Formisano and Cottini assert the PFS data show "Current Life on Mars." This scenario is only one possible explanation as evidenced by their usage of the conditional qualifiers "may" and "can be" at points in the abstract. I will acknowledge, however, that Formisano and Cottini do seem to be leaning towards a biogenic explanation for their observations, though they are being very cautious. And rightly so.
Secondly, neither a conference abstract nor a conference "live" presentation is considered a "publication" since neither has been subjected to peer review. I'll wait to see what and how much of their claims they manage to get through to final publication in, most probably, the journal Nature.
Finally, the usage of "Wimps Out" on the webpage is just another one of TEM's typical tasteless ad hominem attacks.
Posted by: Alex R. Blackwell | September 21, 2004 at 07:04 AM
Dear Alex, Thanks for your comments. I also am very curious about V. Formisano's upcoming Nature article. It should be fascinating reading.
Posted by: Rick L. Sterling | September 21, 2004 at 07:22 AM
That abstract—thanks Rick—is obviously intriguing but also kind of weird. The formaldehyde level is ten times the methane level. As Formisano et al have previously argued, and as they say again in the abstract, one would straightforwardly expect that formaldehyde would be made from methane—whatever the source of that methane—and that because it is much shorter-lived than methane there should be much less of it. Ten times more of it is really hard to explain.
There is an abiogenic route to formaldehyde, I think (solid state photochemistry where ice and dry ice are mingled). But it would be a real shock if that were productive enough for this sort of level. Remember the published earth-based observations, made with a much better instrument than PFS in a much less privileged position, set a limit on formaldehyde of three parts per billion, which is 50 times lower than the level claimed here; unpublished results put the level a thousand times lower.
The abstract suggests a sort of explanation when it mentions the possibility of methanogens and methanotrophs—bugs that make methane and bugs that eat methane. The idea would be, I imagine, that most of the methane produced is immediately consumed and only a very little leaks out of the subterranean ecosystem into the atmosphere. That makes ecological sense, and much of the biologically produced methane on the earth is used up that way. But if the ecosystem hoards its methane why would it chuck out formaldehyde? (If, that is, there was any reason for the bugs to be making formaldehyde in the first place. A more likely product, I'd have thought, would be hydrogen sulfide.)
Which brings us to the fact that the third trace gas mentioned is not, as people had sort of suspected, hydrogen sulfide, but hydrogen fluoride. That's strange, and would kind of have to be either volcanic or a far weirder life-form than any earthly methanotroph or methanogen. And the HF levels are really high; parts per million, not per billion, within an order of magnitude of the amount of water vapour. I've no idea what to make of that.
I hope to have more to say in a day or so.
Posted by: Oliver Morton | September 21, 2004 at 08:57 AM
From Doug Lombardi, on the possibility that Phoenix's mass spectrometer might be modified to detect atmospheric methane:
"We have made a slight modification to the [mass spectrometer] instrument and we are carrying methane detection as a lower priority requirement. However, if during calibration and characterization, operating the instrument in the fashion required to obtain the methane measurement compromises any of the original science requirements or goals, we may need to descope the methane measurement. We do not foresee any reason this should happen. Also, atomic oxygen is still 'in.' " (I imagine this "modification" has something to do with varying the degree of ionization that the M.S. will inflict on the molecules entering it.)
He also confirms that the landing hazard avoidance system will not be carried on Phoenix -- the new website was wrong about that.
By the way -- although he seemed to be alone among the Mars Strategic Roadmap Committee members on this -- Steve Squyres is apprehensive that the near-polar ground ice mantle may actually be so patchy (below the resolution of any of the current Mars orbiters' instruments) that Phoenix may be unlucky enough to land on an iceless area. As he says, though, there's nothing to be done about this in any case.
Posted by: Bruce Moomaw | February 02, 2005 at 02:03 AM
V. Formisano will present his data for Martian Methane & Formaldehyde & Water at the Ist Mars Express Science Conference on Feb. 24,2005. http://www.congrex.nl/05c05/ Click on this link! Then click on the link "Programme"! Then under "Exobiology on Mars" see V. Formisano's presentation listed!
Posted by: Rick Sterling | February 16, 2005 at 06:22 PM
V. Formisano is now stating that as a result of his finding CH4 & Formaldehyde on Mars, there is life on Mars. http://www.newscientist.com/article.ns?id=dn7014
Posted by: Rick Sterling | February 17, 2005 at 01:42 AM
NASA researchers claim evidence of present life on Mars. http://www.space.com/scienceastronomy/mars_life_050216.html
Posted by: Rick Sterling | February 17, 2005 at 01:56 AM
I'll take 2 minutes to tell Senators not to srupopt this Act. I work for a company that supplies consumer products companies with materials, and they are VERY STRICT about the products they recieve and the safety testing involved. Minor changes require months of testing. It is very difficult and often takes welo over a year to introduce an ALREADY TESTED raw material into a new product that we might sell to them.This article is nothing more than scare-monthering. IT is a solution without a problem.By the way, formaldehyde is everywhere. It is present throughout our environment.The purpose of this law is not for the children , but to give greater control over how comapanies do business. It is more central planning and more favoritism for the big guys vs. the little guys.We had a lead issue with toys coming from China. One of the marketers of the toys that contained lead is Mattel. Congress went into action and created new testing methods to prevent lead containing toys from being sold into this country. Guess who is exempted from having their products tested by an independent agency for the presence of lead . . .Mattel. See how great this legilsation works?It sickens me how easily people get sucked into this garbage. We have 9% unemployement close to 20% undermployment or given up, and we watn to have more laws so we can pay more people to push around paper instead of doing something productive. I find it interesting that there are no statistics, no background on the real extent of the problem that this law is supposed to address. If it was that bad, I would think there would be more about it. That doesn't stop you from trying to scare us.
Posted by: Kendall | August 04, 2012 at 10:57 AM
Julius I didn't include a lot of deiltas here, because it would take volumes to elaborate the problem. I just watched the Senate hearing and there is agreement from both sides of the aisle (yes, both political parties) that TSCA needs to be updated and fast. The public health risks are undeniable. Also, a study conducted by Amherst earlier this year actually found that TSCA reform would lead to job creation, not more economic burdens.This is not fear mongering. The need for safer chemicals is fact.
Posted by: Milou | August 04, 2012 at 04:32 PM
Kinikinkick makes GREAT gluten free dtnous! :) Eat up 13! I'm trying to avoid the Halloween candy. I'll be tossing it in the trash before noon. Either that or I'll gobble it up.Perspectivae (we're female and that's the female, nominative plural ending.)Adults have been overlooked because it's parents of kids primarily under 20 who have been able to learn about the diet as the Internet has exploded and parent based groups have started. NAAR was run by psychiatrists and is now Autism Speaks = you can't expect them to discuss diet. It's not in their mindset. TACA, NAA and so many others were founded by MOMs and DADs who saw changes in their kids and demanded to learn more, so they self-taught. Having no where else to go. Even Autism Society of America had little to offer regarding treatment.So you haven't missed the boat, 13/Matt, you're welcome to don a lifevest and settle in next to the rest of us. IF docs can give freaking Viagra to an 85 year old man I should hope they'd realize that adults in all areas deserve proper care.Lord, off my soapbox now! Much to today, starting with cleaning bathrooms. Ah the glamorous life I lead!
Posted by: Vasanth | August 04, 2012 at 07:33 PM