Gerry- You are correct, it does go back further, In this instance I felt the '60's were far enough back to make a point feeling the '85 and '91 papers and other pubs listed in other replies on this topic including yours on this topic were sufficient. Not to mention most of these more recent pubs are obtainable in common and available journals on line and in the library. Besides you mentioned you had difficulties finding some of the older literature so I added one and yes there are more. My point is, this is an old topic that has resurfaced many times and was discussed on the list in 2000 which is on line and available. It's good to check out these things but in this instance the issues of roasting and treatments of bleach and peroxide, etc are not new and not that well hidden. Cheers, Dave At 12:52 PM 1/13/2007, you wrote: >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 >>***********************************************************