Thanks Dave!!!

A few things to note:
It's not available online :(
It goes back a little further, 1953.
It's not listed on the GSA website--there are gaps in available abtracts
If you have trouble digging it up in your library, it's because it's Bulletin of the Geological Society of America until 1960, then it switches to Geological Society of America Bulletin.

take care

gerry


David A. Mucciarone wrote:

Hi folks-

Sorry for this late input on this issue I was going though my numerous emails after on a 2.5 month research cruise and came across this one and I felt I had to respond. Please see the email I posted to ISOGEOCHEM on this topic back in 2000. Gerry good compilation of past emails to the list.

The issue goes back to 1963 by Epstein, Bushsbaum, Lowenstam and yes Urey published in GSA vol 64, p 1315-1326. Titled Purification of calcium carbonate or marine shells.

It is nice that some folks have redone this work and have published it again but these fine scientists who helped form this wonderful stable isotope world thought about this stuff. On page 1318 at the bottom you will read "This procedure converts aragonite to calcite ..... referring to roasting aragonite. Later it states that "The analyses for sample I(d) show a very marked increase in O18 when aragonite transformed to calcite, ..."

Others have done this and found out the same result Grossman et al 1985 (see ref below) Where on page 12 states "... roasted samples are depleted in 18O by 0.4 +/-0.3 ..." he also discusses the affects of bleaching. Dunbar was also an author and years back posed the question to me in 1988 and I did the experiment again at 150'C to 320'C and found the same result (see below).

Another reference form Gaffey, Kolak, and Bronnimann 1991 in Geochimica vol 55 pp 1627-1644 titled Effect of drying, heating, annealing, and roasting on carbonate skeletal material ... I thing Gerry listed this one.

This is not a new phenomenon apparently the information in the older literature gets forgotten or consider to be less important like where did the delta notation come from. Some excellent scientists came before us and shaped the field we are in. Our machines and precision may be better, but these folks overcame a lot to get us where we are today. We can learn a lot and continue to advance from their past work and save valuable time not repeating some of it.

Bottom line - Do not roast aragonite.



Dave


At 07:50 PM 12/7/2006, you wrote:

hI All--

Thanks Bill--this discussion was needed. And any paper on this would be excellent--or perhaps a series of papers (fresh bone, fossil enamel, coral, shells, etc.). Apparently there was a session, formal or informal, at a meeting, don't know which one, in the '70's (?) discussing carbonate treatments--and I haven't been able to find any references to it. Though I did come across a paper doing carbonates on sea shells where the author stated in the methods section that half the people roast, half don’t, and they weren’t because they didn’t know why people were roasting in the first place.

Just a compilation of references, plus a few more at the end that I had dug up earlier--probably some from the Isogeochem archives. I didn’t include the dental studies (Ksp of pulverized enamel--but they didn’t study Coke).

good luck...

gerry

From David Manning:

...We have coupled an IRMS to a thermal analysis system, so we can get on-line analysis of CO2 evolved as a complex material degrades on heating...References (all available on line) that describe this system include:

Lopez-Capel, E., de la Rosa-Arranz, J. M., González-Vila, F. J., González-Perez, J. A. and Manning, D. A. C. Elucidation of different forms of organic carbon in marine sediments of the Atlantic Coast of Spain by thermal analysis coupled to isotope ratio and quadrupole mass spectrometry. Organic Geochemistry, in press.
Lopez-Capel, E, Abbott, GD, Thomas, KM, & Manning, D. A. C. Coupling of thermal analysis with quadrupole mass spectrometry and isotope ratio mass spectrometry for simultaneous determination of evolved gases and their carbon isotopic composition. J ANAL APPL PYROL 75 (2): 82-89, 2006
Lopez-Capel, E, Bol, R, Manning, DAC Application of simultaneous thermal analysis mass spectrometry and stable carbon isotope analysis in a carbon sequestration study RAPID COMMUN MASS SP 19 (22): 3192-3198 2005
Manning, DAC, Lopez-Capel, E, Barker, S. Seeing soil carbon: use of thermal analysis in the characterization of soil C reservoirs of differing stability MINERAL MAG 69, 425-435 AUG 2005

David Manning

From Andrea Grottoli:

I have spent some time thinking about pre-tretment issues regarding the stable isotopic composition of biogenic aragonite. Roasting was shown to cause an unpredictable and uncorrrectable isotopic shift in coral skeletal ä 18 O (Dunbar and Wellington 1981; Gaffey et al 1991; Land et al 1975). I have recently published a paper wherein we conducted a extensive tests of other pretreatment effects (bleach and hydrogen peroxide) on stable isotopes in coral skeletons (Grottoli et al 2005). I have pasted the abstract in below here. We showed that organic carbon is not a source of "contamination" and that pre-treatments cause non-correctable isotopic shifts in ä 13 C and ä18 O that are due to partial dissolution of the carbonate material. I would be happy to provide a copy of the .pdf to any who are interested....

From Max Coleman and Pier de Groot:

Hi Max and others,

The Fritz and Fontes paper ref (indeed in French), is:
Fritz P. and Fontes J. C. (1966) Fractionnement isotopique pendant l'attaque acide des carbonates naturels: rôle de la granulométrie. C. R. Acad. Sc. Paris. t. 263, 1345-1348

The Weber and Deines paper Max refers to probably is:
Weber J. N., Deines P., Weber P. H., and Baker P. A. (1976) Depth related changes in the 13C/12C ratio of skeletal carbonate deposited by the Caribbean reefframe building coral Montastrea annularis: further implications of a model for stable isotope fractionation by scleractinian corals. Geochim. Cosmochim. Acta 40(1), 31-39 doi: 10.1016/0016-7037(76)90191-5

What is not mentioned sofar is that other factors also are important, such as grain size of the acid digested carbonate.



And a few more (ok, some repeats)

Love, K. M. and Woronow, A. 1991 Chemical changes in aragonite using treatments for the destruction of organic material. Chem. Geol., 93:291-301.

Koch, P. L., Tuross, N., Fogel, M. 1997 The effects of sample treatment and diagenesis on the isotopic integrity of carbonate in biogenic hydroxylapatite. J. Arch. Sci., 24, 417-429

Grottoli, A. G., Rodrigues, L. J., Matthews, K. A., Palardy, J. E., Gibb, O. T. 2005 Pre-treatment effects on coral skeletal 13C and 18O. Chem. Geol., 221:225-242

Boiseau, M. and Juillet-Leclerc, A. 1997 H2O2 treatment of recent coral aragonite: oxygen and carbon isotopic implications. Chem. Geol. 143:171-180

Gaffey, S. J., Kolak, J. J., Bronnemann, C. E. 1991 Effects of drying, heating, annealing, and roasting on carbonate skeletal material with geochemical and diagenetic implications. Geochim. Cosmoschim. Acta, 55:1627-1640.

Garvie-Lok, S. J., Varney, T. L., Katzenberg, M. A. 2004 Preparation of bone carbonate for stable isotopic analysis: the effects of treatment time and acid concentration. J. Arch. Sci. 763-776.

Tang, R., Wang, L., Nancollas, G. H, 2004 Size-effects in the dissolution of hydroxyapatite: an understanding of biological demineralization. J. Mater. Chem. 14:2341-2346.

And from some earlier list discussions:

ate: Sat, 25 Nov 2000 12:49:18 -0800
Reply-To: Stable Isotope Geochemistry <[log in to unmask]>
Sender: Stable Isotope Geochemistry <[log in to unmask]>
From: "David A. Mucciarone" <[log in to unmask]>
Subject: Re: Roasting of biogenic carbonates
In-Reply-To: <[log in to unmask]>
Content-Type: text/plain; charset="us-ascii"; format=flowed

For what it's worth, a few years back I was asked if roasting caused isotopic problems to carbonates. Not having an answer other than dogma that I inherited from various colleagues. I decided to do some experiments. I took a couple of calcium carbonate standards and roasted them in vacuum at different temps and for different times. For calcium carbonate I found no real difference in the oxygen or carbon isotopes from 150'C to 320'C the std dev was about 0.1 permil for the entire experiment. However, when I took some aragonite from a couple of corals, I obtained different results. Both temp and time matter for oxygen, however, I saw no real difference in d13C stdev less than 0.1 permil. From 150 to 320 'C there is an isotopic shift of -0.45 permil over time for this entire range. For example at 150'C at 30 min there is an isotopic change in oxygen of approx -0.22 and at 1 hr -0.45 at 1.5hr no change, at 2 hr no change. We feel that since there is probably little benefit of ro! asting aragonites at less than 150'C we decided to no longer roast our coral samples. In Grossman et al, 1986, Marine Micropaleo, 10, 9-22 and in Grossman and Ku, 1986, Chem Geol, 59, 59-74, they discuss this same offset (-0.4 permil) to some extent but they roasted at higher temps To take this one more step. We have duplicated a short isotope record, one set that was previously roasted at 250'C and redone without roasting, we found a consistant -0.45 permil offset for the entire record. I have not done any experiments doing roasting in a carrier stream. So I have no input on this technique. Cheers, Dave **************************************************************************** David A. Mucciarone Laboratory Manager Stanford University Department of Geological and Environmental Sciences Building 320, Room 118 Stanford, CA 94305-2115 650-723-0817 (office) 650-725-2199 (fax) Office - Green Earth Sciences Rm. 331 Stanford Stable Isotope Laboratory - Green Earth Sciences Rm. ! 332 & 334. http://pangea.stanford.edu/isotope/dam/sil_home.htm! l e-mail: [log in to unmask] WWW: http://pangea.stanford.edu/isotope/dam/dam_home.html ****************************************************************************

Date: Fri, 21 Jun 1996 09:01:35 -0500 (CDT)
From: "Scott J. Carpenter" <[log in to unmask]>
To: [log in to unmask]
Subject: Re: Treating organic rich carbonates
In-Reply-To: <v01530500adf00b2b01b9@[129.105.129.11]>
Message-ID: <[log in to unmask]>
Content-Type: TEXT/PLAIN; charset=US-ASCII

Dear listeners: A paper by Gaffey and Bronnimann (1993) -- Effects of bleaching on organic and mineral phases in biogenic carbonates. Journal of Sedimentary Petrology, 63: 752-754 describes what happens to CaCO3 when you attempt to remove organic matter with bleach/Chlorox/sodium hypochlorite and hydrogen peroxide. Hydrogen peroxide dissolves the carbonate more readily than the sodium hypochlorite. A dilute solution of sodium hypochlorite seems to work best. You can examine the SEM images and decide for yourself. -- No geochemical data but... Roasting in vacuo -- surely water is driven off surfaces. Included CO2 and water should also be driven off at approx. 100 degrees above formation temperature. These seem like good things to remove. What is the fate of the organic matter ? Are there reactions which promote carbonate dissolution ? Are there mineral transformations (Aragonite-->Calcite) ? Perhaps these are future topics of discussion. Another fascinating topic would be the! drilling of aragonite (e.g., coral skeletons) with a dental drill and what, if any, isotopic changes occur during this process. so... 1. Wash with a dilute solution of sodium hypochlorite 2. Rinse with distilled water (Repeat 1 and 2 as needed) 3. Roast sample at the mineralogically appropriate temperature in vacuo 4. Dessicate/Store until analyzed. Sincerely, Scott J. Carpenter The University of Texas at Dallas Stable Isotope Laboratory Department of Geosciences P.O. Box 830688 Richardson, TX 75083 Phone: 214-883-2481 Laboratory: 214-883-2632 FAX: 214-883-2537


William Patterson wrote:

Dear Listmembers,
Thank you all for responding (online and offline). I hope you don't mind if I name names herein, and if I misinterpret what you've said please correct it. Although I was hoping for a simple, straightforward, documented and published temperature-isotope shift relationship it appears that the situation is far more complicated. A number of listmembers (myself included) have conducted experiments that remain local lab-lore because as Luis Gonzalez put it "you can't get a PhD or tenure if you publish it". In conversation with Howie Spero, we discussed the possibility of pulling all of this widely disseminated data together into a 50 author methods-type paper. That idea remains open to discussion. We could conduct a multilab evaluation of standardized materials and include that information. I think that David Manning's idea of using a coupled TG-IRMS approach is a good one that can provide us with some information on exactly what is leaving the system during roasting and when. Lora Wingate and Kacey Lohmann have conducted some detailed experiments that will hopefully be published soon, although Lora has provided us with a good summary of what they observed. This is all a bit of a delicate matter to some researchers as Steve Crowley suggested, as some/many data sets will have an inherent offset from others if sample preparation varies. These offsets can be significant particularly those related to paleotemperature calculations

If I may briefly summarize what I've read and heard in conversation off list.
1) Roasting at low temperatures 50-200°C does not seem to influence isotope values except for those of corals.
2) Roasting of marble standards does not seem to result in a shift in values until you get to very high temperatures (perhaps because these standards are pre-roasted by nature?).
3) Roasting of biogenic materials above 200°C or for longer than one hour often (perhaps generally) results in material-specific shifts in isotope values. Calcite values seem more resistant to higher temperatures, while aragonite values vary from a little to a lot depending on temperature and mineralization process. Corals seems particularly prone to complicated variability. I haven't heard anything from cocolith roasters as of yet.
4) Organic matter doesn't seem to be the culprit behind these shifts. While I was a grad student with Kacey Lohmann at Michigan I mixed up some aragonite and calcite slurries with organic matter. The aragonite and calcite carbon isotope values were ~2 and -3 respectively and the organic soup (crushed maple leaves/ Acer rubrum/) had a carbon isotope value of ~-26. Aliquots of these slurries were dried at 50°C. Roasted (200°C) and unroasted slurries were then analyzed in a Kiel device, resulting in carbon isotope values of ~2 and -3 whether they were roasted or not. This suggested to me that roasting at 200°C didn't change the isotope value and that roasting might not be important anyway.
5) I agree/believe with Lora and others that water of some sort adsorbed/structural/fluid inclusions/interstitial/etc. is probably responsible. I don't have any evidence for this, but until it can be discounted, it appears the most viable option. Once David Manning finishes moving his lab we can put him to work on evaluating that hypothesis (just a hint David).
6) Resolving this issue will result in a better ability to compare data sets published in the literature.
7) I could go on...but I have a meeting to go to now...

I thought that I was going to open a small can of worms with my original roasting post. But now it looks more like a cargo container was opened.

Thanks again to everyone one that responded and is interested in this issue.
Cheers,
Bill
--

Dr. William P. Patterson
Professor and Director of the Saskatchewan Isotope Laboratory
Department of Geological Sciences
University of Saskatchewan
114 Science Place
Saskatoon SK S7N 5E2
Canada
Phone: 306-966-5691(office); 306-966-5712(lab)
Email: [log in to unmask]
Web: http://geochemistry.usask.ca/bill.html

***********************************************************
David A. Mucciarone
Stanford University
Dept. of Geological & Environmental Sciences
450 Serra Mall
Building 320, Room 118
Stanford, CA 94305-2115
650-723-0817 (O) 650-725-2199 (F)
http://pangea.stanford.edu/isotope/dam/sil_home.html
***********************************************************

***********************************************************
David A. Mucciarone
Stanford University
Dept. of Geological & Environmental Sciences
450 Serra Mall
Building 320, Room 118
Stanford, CA 94305-2115
650-723-0817 (O) 650-725-2199 (F)
http://pangea.stanford.edu/isotope/dam/sil_home.html
***********************************************************