From: Daniel Hummer Sent: Thursday, February 25, 2016 15:39 To: Liu, Chao; Golden, Joshua J - (jgolden) Cc: Robert Hazen; Knoll, Andrew; Downs, Robert T - (rdowns); Paul Falkowski; Meyer, Michael; Dimitri Sverjensky; Peter Fox; Marshall X Ma; Elisha K. Moore; Sophie Kolankowski; Daniel Hummer; Morrison, Shaunna - (shaunnamm); Grethe Hystad; Edward Grew Subject: Re: Nitrogen mineral evolution: to mineral evolution group Chao, That's a fantastic idea. Maybe we can try making age histograms and accumulations curves for sets of more common evaporite minerals like halite, sylvite, gypsum, etc., and compare to see if they follow a similar trend. Dan Daniel R Hummer Postdoctoral Scholar, Mineralogy and Crystallography Geophysical Laboratory Carnegie Institution of Washington Phone: (814) 321-8859 Fax: (202) 478-8901 On 2/25/16 3:23 PM, Liu, Chao wrote: Hi all, If preservation is a big issue for N-minerals, it might worth searching and compiling age-locality information of all evaporitic minerals as a comparison. Chao ------------------------------------------ Chao Liu Postdoc Associate Carnegie Institution for Science 5251 Broad Branch Road NW Washington, DC 20015 On Thu, Feb 25, 2016 at 1:40 PM, Golden, Joshua J - (jgolden) wrote: Dear all, The cumulative distribution graph of N minerals is a preliminary account of the data thus far contained in the Mineral Evolution Database (MED). I have not looked specifically for the age of the N bearing minerals at the dated localities, so the N minerals may be younger than what is in the graph. Only 51 of the 103 N minerals have at least one dated locality in the database. I agree that it is likely too early to tell much from the cumulative curve without looking in detail at the data. I thought that since the curve was so different than the rest of the elements curves based on the same data within the MED that there might be something interesting to be seen from the N data, specifically in the last ~500 My. Perhaps the availability of N from the atmosphere increased as well as increasing solar (EM) radiation reaching the surface after the melting of the last snowball Earth. The population of the land by plants around 450 Ma and the diversification of land plants at around 430 Ma occurs just before the first major spike on the graph (~416 Ma) for NH4 minerals. Though, more precise data is needed. May be worth coming back to in the future. Best Regards, Josh From: Robert Hazen Sent: Thursday, February 25, 2016 10:12 AM To: Knoll, Andrew Cc: Downs, Robert T - (rdowns); Paul Falkowski; Meyer, Michael; Golden, Joshua J - (jgolden); Dimitri Sverjensky; Peter Fox; Marshall X Ma; Elisha K. Moore; Sophie Kolankowski; Daniel Hummer; Chao Liu; Morrison, Shaunna - (shaunnamm); Grethe Hystad; Edward Grew Subject: Re: Nitrogen mineral evolution: to mineral evolution group Dear Colleagues, I've spent a couple of hours surveying nitrogen minerals. In fact there are 103 N mineral species, of which 6 are nitrides found in meteorites. Joshua's graph (as I should have known) included 52 species for which we have ages. I've done a detailed survey of the first 26 minerals in the ruff.info/ima list. Half of them are ammonium minerals, mostly sulfates, from fumaroles (volcanic sublimates) and/or from burning mine minerals. A remarkable 12 N-bearing minerals have their type locality at the La Fossa fumarole of Vulcano, Italy (most of those are unique occurrences at Vulcano). Several more minerals come from oil shale, black shale, or coal. Other paragenetic modes include guano, hot springs, evaporites, and alteration zones of ore bodies. My impression is that almost all of these phases are ephemeral and associated with Phanerozoic biological processes. Have to do some more digging to find how the Archean and Proterozoic ages fit this picture, but I'm guessing that most of the N minerals are very late stage precipitates or alteration products. Still may be a very interesting story to tell, but can't be sure yet what it is. Will put this on the back burner for now. Best, Bob On Thu, Feb 25, 2016 at 11:07 AM, Knoll, Andrew wrote: Bob – that was my thought, exactly. A preliminary scan of nitrogen minerals shows many of them in environments not well represented in the geologic record. I agree with Bob H that it will be useful to work through these occurrences one by one, with eyes wide open. Andy From: Downs, Robert T - (rdowns) [mailto:rdowns@email.arizona.edu] Sent: Thursday, February 25, 2016 11:01 AM To: Robert Hazen; Paul Falkowski Cc: Knoll, Andrew; Meyer, Michael; Golden, Joshua J - (jgolden); Dimitri Sverjensky; Peter Fox; Marshall X Ma; Elisha K. Moore; Sophie Kolankowski; Daniel Hummer; Chao Liu; Morrison, Shaunna - (shaunnamm); Grethe Hystad; Edward Grew Subject: RE: Nitrogen mineral evolution: to mineral evolution group Hi Bob, Let me throw something out there about the trend that is near linear, NO3 compounds I believe. I wonder if the linear pattern could be the indication that this is a set of minerals that do not survive well over time. The compounds with spikes in their graphs seem to indicate that there is no appreciable “weathering” of the minerals, else the spike would not persist. Anyway, just a thought. Bob From: Robert Hazen [mailto:rhazen@ciw.edu] Sent: Thursday, February 25, 2016 7:22 AM To: Paul Falkowski Cc: Knoll, Andrew ; Meyer, Michael ; Golden, Joshua J - (jgolden) ; Downs, Robert T - (rdowns) ; Dimitri Sverjensky ; Peter Fox ; Marshall X Ma ; Elisha K. Moore ; Sophie Kolankowski ; Daniel Hummer ; Chao Liu ; Morrison, Shaunna - (shaunnamm) ; Grethe Hystad ; Edward Grew Subject: Re: Nitrogen mineral evolution: to mineral evolution group Dear Paul and Andy, Thanks for the perceptive messages. Yes, we have to look at every N mineral species carefully: each locality and occurrence, and the paragenetic contexts. That's a lot of work, but exactly what I've been doing for the 66 cobalt minerals. Since there are only 52 N minerals, I could do a first pass through all of them in a day. Not today, but maybe soon. So this will be straightforward to a point, and then we can see what the data tell us. Still, to me the most interesting initial aspect is that this is the first system (with the exception of sedimentary carbonate minerals) that doesn't follow the supercontinent cycle. Question: since we now know that hydrogen forms abundantly in serpentinization reactions, does ammonium form as well under near-surface conditions? Has anyone studied that? More to come. Best, Bob On Wed, Feb 24, 2016 at 9:57 PM, Paul Falkowski wrote: Dear All, Yes, interesting - but I am not sure how these minerals formed - and that is critical to interpreting their potential bio/geo connection. We think that, absent biology, the only source of nitrogen ions would have been from lightning - forming a relatively small amount of oxidized nitrogen (nitrite and perhaps nitrate). We also think that Earths early atmosphere contained N2 gas - not ammonium. The turnover time of N2 in the atmosphere is about 1 billion years - So - given these constraints - if real - we should have a sequence that obeys 1. the redox state of N in the minerals 2 the the availability (i.e. concentration of N ions in the envionment) 3. the reaction of the ion to form a mineral. Obviously ammonium ions can substitute for Na, K, or any other group I elements - and that can be done at low temperatures by hydrothermal contact. I am not sure how nitrates can be formed - as these have almost certainly have to be evaporites - nitrate could never have reached supersaturation in the oceans or any aquatic environment on Earth’s surface at any time. Could someone please walk me through a genesis of the N bearing minerals - to the best of your knowledge. Are there other co-minerals? For example - evaporites - or clay minerals - that can tell us whether we are going down a rabbit hole or are really on to something significant? Cordially, Paul On Feb 24, 2016, at 11:11 AM, Knoll, Andrew wrote: It IS interesting, but I would be very, very (did I mention vey) careful to account for record bias before interpreting this in any detail. It is worth asking what processes give rise to specific N minerals and how we would expect them to be distributed in time and space. Guano, mentioned by Bob, is a good example. Cheers, Andy From: Meyer, Michael [mailto:mmeyer@carnegiescience.edu] Sent: Wednesday, February 24, 2016 9:49 AM To: Robert Hazen Cc: Joshua Golden; Bob Downs; Paul Falkowski; Dimitri Sverjensky; Knoll, Andrew; Peter Fox; Marshall X Ma; Elisha K. Moore; Sophie Kolankowski; Daniel Hummer; Chao Liu; Shaunna Morrison; Grethe Hystad; Edward Grew Subject: Re: Nitrogen mineral evolution: to mineral evolution group This is really interesting data. I'm very interested in the jumps in the N curve ~600 mya and shortly into the Phanerozoic (maybe ~400 mya). Those spikes may match diversification events. There may also be some extinction signals, such as the late Devonian extinction event or the Permo-Triassic extinction (in the little plateau ~250 mya). There is definitely some potential for this! On Wed, Feb 24, 2016 at 9:30 AM, Robert Hazen wrote: Dear Colleagues, I recently got the following message with attached graph from Josh Golden: "I came across an interesting 1st occurrence cumulative distribution curve for nitrogen minerals. What was interesting about it is that it did not seem to have the same pattern as the rest of the elements. The spikes in diversity at about 2700 Ma and at the end of the GOE at about 1900 Ma seen in the other elements do not exist in the nitrogen data. I now have a cumulative distribution curve plotted for all 72 mineral forming elements. ... The nitrogen anomaly may be real. I plotted accumulation curves for all N minerals, NH4 minerals, NO3 minerals, and the remaining other N minerals together and the results are very interesting. It seems that the NO3 minerals do not show spikes in mineral diversity like other elements or even NH4 minerals. The NO3 curve is apparently nearly linear. I have attached the graph to this email." Not sure why we didn't look at minerals of N (or P, for that matter, for which we have a lot more mineral data) before. Perhaps the concern was that nitrogen minerals are relatively rare and many appear to be taphonomically derived and ephemeral. We see clear evidence for guano minerals, for example, in the tail-end spike for the past 100 million years. But the trend Josh has found is strikingly different from those for any of the metal elements, all of which so far have shown marked episodicity, probably reasserted to the supercontinent cycle. We've got a lot on our plate right now, but I think the nitrogen story could provide a wonderful way to link our several nodes of the Keck project. So can I ask you to think about what questions are most central to investigating this story, and how we might tackle the next steps. Once I finish cobalt I may take that excursion. Josh: for you, how many dated N minerals do we have? What does the histogram look like? How many mineral-locality pairs are there? I doubt that we can fit an LRNE frequency distribution to those limited data, but we'll see. For Chao: when can we do a deep-dive search for the 52 N mineral species? By the way, please forward this message to team members I didn't include. Thanks, Bob PS: I hope that a lot of us can converge on RPI on June 8-10 for a "data science day". That would be a great opportunity to discuss this and other science projects. -- Robert M. Hazen Senior Staff Scientist, Geophysical Laboratory Executive Director, Deep Carbon Observatory 5251 Broad Branch Road NW Washington, DC 20015 phone: 202-478-8962 e-mail: rhazen@ciw.edu Personal web site: http://hazen.gl.ciw.edu DCO website: deepcarbon.net Keck Deep-Time Project website: http://dtdi.carnegiescience.edu