Diatom Dissolution Replies Collated by Kurt Haberyan Biology Dept, NW Missouri State Univ, Maryville MO 64468 USA 0100730@acad.nwmissouri.edu Note: Below I post the original inquiry about the dissolution of diatoms. Each reply has been posted and (in some cases) edited, with permission of its author, and includes his/her direct e-mail address. In the case of inadvertent changes in meaning, I apologize and will correct the error as soon as I'm notified. I can also add new messages if that is warranted. I'm missing 'permission to post' from a few people; if you contri- bution is not here and you'd like it to be, let me know. Thanks to all! Kurt 0100730@acad.nwmissouri.edu - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - THE ORIGINAL QUERY - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - On Wed, 29 Jan 1997, HABERYAN wrote: Greetings, fellow diatomists! I'm still working with these recalcitrant sediments from Costa Rica and have encountered another 'challenge.' One of the longest and most interesting cores only has diatoms near the top, but sponge spicules throughout. There are fragments of diatoms on the slides, but these too become more common upcore. Dissolution is clearly a major factor. What kinds of conditions enhance dissolution? I remember a 'roundtable' discussion at the Diatom Symposium in Philadelphia (1983?) in which it became clear that there's no one answer. Would anyone be willing to comment to me (don't reply to the LISTSERV), or direct me to the important references (and/or send reprints)? Is there ANYTHING we can conclude from the lack of diatoms? Thanks for the help! Kurt Haberyan 0100730@acad.nwmissouri.edu - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - THE REPLIES - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - From: SMTP%"pasiv@conncoll.edu" Date: Wed, 29 Jan 1997 From: "Peter A. Siver"Dear Kurt, I have found through our examination of 60+ lakes in Connecticut that dissolution is mostly a problem in our alkaline lakes. I think this is a real problem for us under these circumstances. Also, one other comment. Are you sure its really dissolu- tion? Or is everything broken into small fragments? I often check closely with SEM to see if the silica fragments are really "etched" or not. In a few instances we had all broken fragments, but the scaled chrysophyte scales were in great shape - thus, no dissolution problem here. Peter Siver - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - From: SMTP%"slcooper@acpub.duke.edu" Date: Wed, 29 Jan 1997 From: Sherri Cooper Kurt, I am also finding the same thing in some cores from the Everglades. I think that in our case it has something to do with organic acids. (See Bennett et al. "Fate of silicate minerals in a peat bog" Geology, v. 19, pp. 328-331 (1991)). Although with the sponge spicules present, not sure what is going on... we also have the same thing in many samples. I know that it is not strictly a pH problem in our case. Best wishes, Sherri Cooper Duke Wetland Center Box 90333, Durham, NC 27708 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - From: SMTP%"haskell@maroon.tc.umn.edu" Date: Wed, 29 Jan 1997 From: Brian Haskell Hello Kurt, Silica tends to be undersaturated in just about all systems, so a tendency towards dissolution is a given. Dissolution is also affected by pH, and very strongly affected by temperature. I did a quick search on my references database and came up with the following references that might have bearing on your question on the listserver. Thayer, V. L., T. C. Johnson and H. J. Schrader, A preliminary study of recent diatom assemblages in Lake Superior sedi- ments, Journal of Great Lakes Research, 9, 508-516, 1983. Barker, P., J.-C. Fontes, F. Gasse and J.-C. Druart, Experimental dissolution of diatom silica in concentrated salt solutions and implications for paleoenvironmental reconstruction, Limnology and Oceanography, 39, 99-110,1994. I have done some silica dissolution as part of other studies and sponges are very resistant to dissolution. I am not sure why this is, although the low surface area/volume ratio might account for it. Might there be a difference in the opal structure (guessing)? Cheers, Brian J. Haskell Telephone: Limnological Research Center (612) 624-7005 University of Minnesota (612) 378-3242 310 Pillsbury Drive. S.E. Fax: Minneapolis, MN 55455-0219 (612) 625-3819 http://lrc.geo.umn.edu/people/haskell/ - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - From: SMTP%"bsgeol@u.washington.edu" Date: Wed, 29 Jan 1997 From: Brian Sherrod I have read that when conditions are too alkaline, diatom frustules can dissolve. I wonder if the same is true for high pH's??? Try looking at Mikkelson, N., 1980. Experimental dissolution of Pliocene diatoms. Nova Hedwigia, 33(2): 893-911. Brian Sherrod Department of Geological Sciences/USGS University of Washington, Box 351310 Seattle, Washington 98195 bsgeol@u.washington.edu (206)685-1960 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - From: SMTP%"msvd@opal.geology.utoronto.ca" Date: Wed, 29 Jan 1997 From: "M.S.V. Douglas" 9 (Andrejko and Cohen 1984). Dissolution also occurs in environments such as peats which have no minerogenic input other than atmospheric inputs. In those cases, silica is in such demand that it is used up by living organisms. ie., the material is undersaturated with respect to silica. 2. Dissolution of diatom valves was evident and sponge spicules showed evidence of dissolution and borings. Andrejko et al (1982) have shown these borings and pitting to be present in sponge spicules and attribute this to bioerosional features originating from organisms such as fungi and possibly diatoms (!). 3. Andrejko, M.J., R. Raymond Jr, A.D. Cohen. 1982. Scanning electron microscopy observation features on freshwater sponge spicules. Scanning Electron Microscopy. II:629-638. 4. Andrejko, M.J and A.D. Cohen. 1984. Scanning electron microscopy of silicophytoliths from the Okefenoke swamp-marsh complex. pp 466-491. In Cohen, Casagrande, Andrejko and Best (Eds). The Okefenokee Swamp: Its natural history, geology and geochemistry. Wetland Surveys. Los Alamos. Marianne Douglas Department of Geology University of Toronto 22 Russell St 416 978 3709 (voice) Toronto, ON 416 978 3938 (fax) M5S 3B1, Canada msvd@opal.geology.utoronto.ca - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Date: Thu, 30 Jan 1997 From: Hedy Kling Hi Kurt, Both high pH and increasing temperature, plus low Si in the interstitial water near the sediment-water interface, enhance dissolution. See the following papers: Lawson, D.S. D.C Hurd and H.S. Pankratz. 1978. Silica dissolution rates of decomposing phytoplankton assemblages at various temperatures. Amer. Jour. Sci. 278:1373-1393. Hecky, R.E. H.J. Kling and G.J. Brunskill. 1986. Seasonality of phytoplankton in relation to silicon cycling and interstitial water circulation in large shallow lakes of central Canada. Hydrobiologia 138:117-126. Another place you may find dissolved diatoms is a deep lake that is very oligotrophic, with low soluble reactive Si concen- tration and low biomass of diatoms. Much of the diatom is dissolved before it reaches the bottom. With low productivity, the diatom may not be buried for quite a while, so dissolution will tend to be more pronounced, so all you find are the thickest parts. Also, once the external organic membrane is off of the diatom, it can start dissolving (even if still living). This happens in Si limited conditions under increased P. Kling H.J. 1992. Valve development in Stephanodiscus hantzchii Grunow (Bacillariophyceae) and its implications on species identification. Diat. Res 7(2) 241-257 p 248. There's a bit more in my paper and Gensemer's papers on Asterionella: Kling H.J. 1993. Asterionella formsa Rahlfs: the process of rapid size reduction and its possible ecological significance. Diatom Res. 8(2) 475-479. Bob Gensemer confirms my hypothesis in his paper in the last proceeding of the international Diatom Meeting: Gensemer, R.W., R.E.H. Smith, and H.C. Duthie. 1994. Interactions of pH and aluminum on cell length reduction in Asterionella ralfsii var. americanum Kormer. Proc. 13th International Diatom Symposium, D. Marino & M. Montresor (eds), pp. 39-46. Hope this helps a bit. Cheers, Hedy - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Date: Thu, 30 Jan 97 From: David Ryves Dear Kurt, I looked at diatom dissolution for my PhD (from which nothing as yet has been published). I was working on the Northern Great Plains of America, in the same lakes and on the same flora as Sheri Fritz, Steve Juggins and Rick Battarbee. My angle was trying to quantify dissolution and modify the salinity transfer function to take into account susceptibility to dissolution; now I'm working on a small project to recount those surface sediment samples and modify the transfer function "at source" in the calibration dataset. To answer your questions, the single most important factor affecting diatom dissolution is pH - above about pH 9 and silica dissolves extremely rapidly and often completely. Other factors can be important though: if diatom valves are dissolving slowly over an extended time dissolution can be equally extensive. For example, diatoms in sediments are often preserved as pore water silica concentrations become saturated; but if there is pore water movement (due to geohydrological conditions or bioturbation perhaps) then pore waters may remain undersaturated with respect to SiO2 and dissolution contines until such time as that equilibrium is established. Breakage also speeds up dissolution rate; there is some interconnection as dissolved valves break more easily, which then dissolve more rapidly... In Lake Baikal, most of the (considerable) dissolution appears to happen at the oxic sediment-water interface; while in a marine context, something like 90% of the silica is lost during sedimentation to the sediment surface, and something in the order of 1% (I think?) actually gets incorporated into sediments. There are also factors associated with the age of diatom silica (it slowly recrystallizes into more insoluble forms; over hundreds of thousands or millions of years though); salinity (dissolution rate is reduced as salinity increases); temperature (again, kinetic dissolution rates increase with temperature). Add to that the differential susceptibility of differently shaped diatom valves to dissolution and the complexity of diatom dissolution becomes apparent. Another (!) consideration is the treatment diatoms get in the laboratory - there can be considerable breakage & dissolution from standard preparation techniques (such as the usual hot hydrogen peroxide treatment we give valves here!); which can be a really exacerbating problem if valves are already partly dissolved and/or fragile to start with. For Baikal material, for example, we now just add water to wet sediment and make slides up directly; but then there is far less organic matter in these sediments than most. Another option would be to use cold peroxide over a day or two. Acid cleaning also makes valves more susceptible to dissolution by removing the metal ions from the silica surface, which retard dissolution (as shown by Joyce Lewin and others since e.g. Phil Barker). I hope some of this is of interest and use for your core material. All the best, David Ryves Environmental Change Research Centre Department of Geography, UCL, UK - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Date: Fri, 7 Feb 1997 From: Philip Barker Kurt, As you note there is nothing simple about diatom dissolution. Most of the factors you mention (pH, pore water silica etc) are the usual culprits but the answer will be site-specific. You don't mention anything about the water chemistry or the nature of the sediments in which the diatoms are absent. If your lake is of the Na2-HCO3-CO3 type then high alkalinity is the most likely explanation. If you have a situation where Ca(Mg)CO3 is precipitating, the resulting chemistry can be very hostile to SiO2. If it is very deep, e.g. Tanganyika, pressure could be a catalyst. The sponge spicule issue is a bit more puzzling. It could be due to spicules having (a) higher density silica (b) a lower surface area/volume ratio than diatoms (c) the spicules are more easily identifiable than diatoms when partially dissolved (d) metals are taken into the sponge silica. A longer shot might be that ambient silica concentrations are higher in the benthos than in open waters, but this would also preferentially protect benthic diatoms. If you want to take this further send me some data and we could put something together. My publications to date on dissolution are as follows: Barker, P.A., Fontes, J.-Ch., Gasse, F., and Druart, J.-Cl. 1994. Experimental dissolution of diatom silica in concentrated salt solutions and implications for palaeoenvironmental reconstruction. Limnology and Oceanography 39: 99-110. Gell, P, Barker, P, DeDeckker, P, Last, W and Jelicic, L. 1994. The Holocene history of West Basin Lake, Victoria, Australia; chemical changes based on fossil biota and sediment mineralogy. Journal of Palaeolimnology 12: 235-258. Barker, P.A. 1992. Differential diatom dissolution in Late Quaternary sediments from Lake Manyara, Tanzania: an experimental approach. Journal of Paleolimnology 7 (3): 235-251. Cheers, Phil - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - From: SMTP%"aritko@utu.fi" Date: Thu, 30 Jan 1997 Kurt, You are probably aware of the information in the following texts: Jones, B.F. & C.J. Bowser, 1978. The mineralogy and related chemistry of lake sediments. In A. Lerman (ed.), Lakes - chemistry, geology and physics. Springer-Verlag, N.Y.: 179-235. Engstrom, D.R. & H.E. Wright Jr., 1984. Chemical stratigraphy of lake sediments as a record of environmental change. In E.Y. Haworth & J.W.G. Lund (eds), Lake sediments and environmental history. Univ. Minnesota Press, Minneapolis: 11-67. This one is even older, but I think its is the most complete of these three: Merilinen J. 1973. The dissolution of diatom frustules and its palaeolimnological interpretation. Univ. of Lund, Dept. of Quat. Geol. Report 3: 91-95. Cheers, Arto Arto Itkonen Department of Geology University of Turku IN-20014 University of Turku Finland tel. +358-2-3336389 fax. +358-2-3336580 e-mail aritko@utu.fi