This rather unassuming photo is included for all you cetophiles out there (or, should that be cetaceophiles? Whatever). These rather crappy fossils represent an assortment of odontocete fragments from the Red Crag deposits of Suffolk, England. I initially thought that I recognised the rostrum fragments (the bigger fossils over on the right) from Richard Owen's 1870 Monograph of British Fossil Cetacea of the 'Red Crag', but I was mis-remembering, as the specimens described therein are housed in the Natural History Museum in London, not the Sedgwick Museum in Cambridge (where this photo was taken).
Two of the specimens are labelled Choneziphius planirostris (Owen used the name Ziphius planus Owen, 1870 for that species, but it proved synonymous with Z. planirostris Cuvier, 1823, later given the genus Choneziphius Duvernoy, 1851)*. Choneziphius is a unique ziphiid (Ziphiidae = beaked whales) in which the mesorostral gutter is dorsally closed at its posterior end by the elevated lateral processes of the premaxillae. It seems to be closely related to Tusciziphius from the Pliocene of Italy and the extant, globally occurring taxon Ziphius (Muizon 1991, Lambert 2005). Numerous Choneziphius specimens are known from the Upper Miocene of Belgium and England and a second species, C. macrops (originally Proroziphius macrops Leidy, 1876), is known from South Carolina.
* If you have very good eyesight, you might be able to see that one of the specimens has been labelled Mesoplodon longirostris. I really don't want to even start discussing the history and eventual fate of this name - anyone else have the time to do it? [non-fossil partial rostrum of the bizarre Mesoplodon layardii shown below, photographed at the University Museum of Zoology, Cambridge. A partial Narwhal Monodon monoceros skull is in front of it].
Worth noting here is that fossil ziphiid rostra have proved relatively abundant in Neogene fossil samples dredged from the bottoms of various sea floors; furthermore, these rostra evidence surprisingly high diversity for this group. Bianucci et al. (2007) described an assemblage of partial rostra and other skull remains dredged from the sea floor off South Africa, and reported an incredible eight new genera and ten new species in this one study alone (Microberardius africanus, Izikoziphius rossi, I. angustus, Khoikhoicetus agulhasis, Ihlengesi saldanhae, Africanacetus ceratopsis*, Nenga meganasalis, Pterocetus benguelae, Xhosacetus hendeysi and Mesoplodon slangkopi). Alas, so much more to say, but I must resist.
* The second recently named fossil odontocete that has a dinosaur-themed name :)
So, I only said things about ziphiid rostra - what are the other cetacean fossils you can see in the photo?
For previous Tet Zoo articles on ziphiids and other odontocetes, see...
- Santa Cruz's duck-billed elephant monster
- Skull of the Moore's Beach monster revealed!
- On identifying a dolphin skull
- Weird whales grand finale
- A Russian sea monster carcass is claimed to be that of an ancient 'archaeocete' whale
- The newest whales
Refs - -
Bianucci, G., Lambert, O., & Post, K. (2007). A high diversity in fossil beaked whales (Mammalia, Odontoceti, Ziphiidae) recovered by trawling from the sea floor off South Africa Geodiversitas, 29 (4), 561-618
Lambert, O. 2005. Systematics and phylogeny of the fossil beaked whales Ziphirostrum du Bus, 1868 and Choneziphius Duvernoy, 1851 (Mammalia, Cetacea, Odontoceti), from the Neogene of Antwerp (north of Belgium). Geodiversitas 27, 443-497.
Muizon, C. de 1991. A new Ziphiidae (Cetacea) from the Early Miocene of Washington Sate (USA) and phylogenetic analysis of the major groups of odontocetes. Bull. Mus. Natn. Nat., Paris (4e sÃ©r.) 12, 279-326.
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"Cetophile" could mean just "sea monster fan", Latin cetus being rather unspecific. Actually seems like a useful word to have.
Oh, right. I had assumed (as most people probably do) that 'cetus' specifically means 'whale'.
That thing is really bizarre - without the article and caption, I might have assumed somebody was trying to mock up an alien.
Is that an Ontocetus tusk in the middle?
Okay, seriously, what were those wing-teeth for?
Maybe Svante PÃ¤Ã¤bo and his team at the Max Planck institute will be able to map the genomes of these extinct cetaceans...unfortunately, these specimen have been stored in sub-optimal conditions, but there must be plenty of other bones on the sea floor.
Zach, those big teeth only erupt in the males, and are used for intraspecies combat. The males rake each other with the teeth; adult male beaked whales are typically covered with linear scars.
Yeah, that's definitely a big Ontocetus tusk in the middle; its short, fat, and curved just like the Yorktown material in Kohno and Ray 2008 (rather than long and straight and less inflated in the 'middle' like in Odobenus).
I'll venture that ziphiid rostra are so 'common' in certain deposits due to their extreme density and the ease that they get left behind in lag deposits, such as the Red Crag; additionally, really dense cetacean ear bones are 'common' in the Red Crag (and there are a multitude of taxa represented).
Whereas it seems that in the case of Bianucci et al. 2007, they reported bone-bearing phosphate nodules that had been trawled from the seafloor from unknown Neogene strata, representing pretty much only ziphiids, and a shit-ton of them at that (numerically and taxonomically).
Oddly enough, there appears to be a genuine lack of ziphiids in the NE Pacific fossil record (there are a few, isolated occurrences), totally unlike the North (and now apparently south) Atlantic (and Mediterranean, and SE Pacific) Neogene, and I don't know why (but it's a really, really interesting phenomenon).
The big, Ontocetus-like tusk is labelled Trichechus, which was of course used for Odobenus until well into the 20th century.. so it seems they have it identified as walrus at least. Olivier Lambert told me yesterday that there's a load of work still to do on the dredged seafloor ziphiid specimens. I meant to include a comment on the extreme density of ziphiid rostra and on how this helps them be so resilient to destruction. One example: the rostrum of Blainville's beaked whale Mesoplodon densirostris is said by some authors to be the densest vertebrate tissue: yes, even denser than ivory.
How dense is that, numerically? I seem to recall that "standard" density for mammalian bone is ~1.9 kg / dm^3 .
In M. densirostris, we're talking about 351 mg of calcium per gram, or a density of 2.3-2.6 g per cubic cm. Ivory is 1.81 g per cubic cm. These figures are all from...
MacLeod, C. D. 2002. Possible functions of the ultradense bone in the rostrum of Blainville's beaked whale (Mesoplodon densirostris). Canadian Journal of Zoology 80, 178-184.
Fascinating article. Out of curiosity I followed up the citations and found that Bianucci et al. (2007) is slightly wrong - that paper is actually in Geodiversitas 29(4): 561-618.
I do quite a lot of deep-sea sampling as part of my work, so I'll certainly be looking out for beaked whale bits from now on!
@Darren #11: Thank you
Dave (comment 12) - the Bianucci et al. reference was generated automically by 'Research Blogging'. I'm trying to correct it.
A couple questions for you Darren, if you have a minute?
What depth do they tend to dredge for these, and is there a lower limit to the depth that these would stay cohesive enough without the calcium phosphate dissociating into the surrounding seawater? Under those pressures it seems that the dissolution would be relatively rapid, or that the bones would be predated upon by specialists of the type common at most whale-fall sites?
In a similar vein, are there any well known whale (or even sauropterygian) fall sites preserved in the fossil record that have been uplifted and discovered terrestrially?
IIRC there are a couple of preserved whale falls from the Neogene of the North Pacific. I think Goedert and/or Pyenson have published on them, but it has been awhile since I have glanced at the papers.
Kohno, in his contribution to the Lee Creek volume, synonymous almost all the fossil walrus from the North Atlantic into Ontocetus. Although most really are of too poor a material (like the tusk shown here) to ever have considered them as valid species to begin with.
How much is a shit ton, exactly?
@Dawn- "The shit ton is a unit of weight equal to 2,000 pounds (907.18474 kg). In the United States it is often called simply ton without distinguishing it from the metric ton."
@Daniel- I think a key parameter is also rate of burial, right? Don't those whale bones get chowed down on pretty hard by everything from microbes to worms? Althought perhaps those just go for the marrow, leaving most of the bone left.
Also, since the ocean gyres have very slow sedimentation rates compared to upwelling or continental shelf regions (and assuming being buried slows or stops bone degradation), any depth-related dissolution will also depend on where the whale falls- and the gyres also tend to lie over the deepest regions of the oceans (abyssal plains).
So, for deep, quick-sedimenting regions, you are left with possibly the equatorial upwelling belts, and places like the Peru trench: trenchs underlying eastern-boundary-current upwelling.
This might qualify Darren's statement of whale bones being "everywhere"- if the above assumptions hold then really they would be found on the continental shelves and upwelling regions, still a substantial area.
@US measurement units: ooh, burn.
Daniel: Regarding dissolution... not much is known for really deep waters. However - I can say that on many shelfs, especially those where upwelling is occurring - the opposite of CaPh dissolution is happening - many shelves where upwelling is occurring are also undergoing phosphogenesis, which results in the 'precipitation' of additional phosphate minerals within the bone, and the development of phosphate nodules around the bones (such as the South African dredged ziphiids).
I'll also mention that most shelves undergoing upwelling and phosphogenesis are actually undergoing close to zero net sedimentation and in many cases, negative net sed.
So, to answer your question - the Red Crag material shown above was collected from a cliff exposure (although some probable red crag material has been dredged from the north sea, and other units too), while the dredged fossils from south africa all occur in phosphate nodules. Thus, in the environment of deposition of the S. Africa beaked whales, there was a chemical environment that was saturated WRT phosphate, allowing phosphate nodules to form and grow (thus, addition rather than subtraction of phosphate).
WRT bone bioerosion - all of that has only been documented from modern (and a couple fossil) whale falls. And yes, there are now many, many fossil whale falls known from the Paleogene and Neogene of California, Oregon, Washington, and Japan. In cold arctic waters it is also possible to have whale falls occur on the middle-outer shelf.
Hm. Is it acellular? Acellular bone (aspidine) is found throughout a clade of early Paleozoic jawless vertebrates.
@Boesse- actually, good point, the artic and near-arctic abyssal plains also have relatively higher sedimentation rates. As far as net rates on shelves, I don't know what percentage of shelves experiment negative net sedimentation, but if mass redistribution to the outer shelf and slope via slides and turbidites occurs that would still keep the bones buried right?
Phosphatization occurs in especially high sedimentation rate areas as far as I know, S. Africa being one such place, where the sediment is anoxic at basically the sediment-water interface. Something to do with microbial dissimilatory nitrate reduction to ammonia (DNRA): http://www.nature.com/nature/journal/v445/n7124/full/nature05457.html
which has proved an excellent way to preserve even tiny fossils: http://www.pnas.org/content/97/9/4457.full
Also, under certain conditions, in-situ carbonate precipitation occurs, such as at the sulfate-reduction/methanogenesis transition zone in organic-rich sediments.
However, there are also subseafloor geochemical conditions that can reduce pH dramatically right- or is it change total-CO2 - that are bad for carbonate preservation right? Perhaps the sulfate-reduction zone, where lots of sulfide and acidity is produced?
whoops, didnt notice the first ref argues against the main point of the second paper- that the microfossils in the second paper are Beggiatoa bacteria and not stem animals- that I don't think is the consensus in the field today. But what it says about phosphatization still holds..
AD - Almost every shallow marine phosphatic deposit (modern or ancient) I have ever heard of was formed due to low (or zero, or negative) net sedimentation, i.e. in many cases by transgressive lags or "condensed sections". Phosphatization almost inherently requires a depositional hiatus in order to require enough time to phosphatize anything (with a few aberrant exceptions, like Santana Fm. fish). WRT negative net sedimentation - the majority of 'fossil' transport on shelves are via erosion, 'bedload' transport and subsequent deposition, which is inherently really damaging to fossil material.
More CO2 in water = more carbonic acid ( = H2CO3) = lower pH.
Gases are better soluble in cold than in warm water.
@David- I think I was getting it mixed up with total alkalinity, which doesn't change with addition of CO2 to a solution.
However, alkalinity will change when acid, such as CO2->H2CO3, is exposed to carbonate. The acid will dissolve the carbonate, releasing (initially) CO3-- which changes total alkalinity.
So apparently it can get fairly complicated depending on what metabolisms are present in the sediment, rate of diagenesis, buffering capacity of the sediment porewater, etc- factors which in turn can be looked at as secondarily dependent on rate of sedimentation, rate of iron input, etc.
But, it seems carbonate preciptation occurs in a variety of circumstances. Extensive zones of methanogenesis in organic-rich sediments can precipitate carbonates due to uptake of protons and CO2 to make methane. Sulfate-reducing heterotrophic or anaerobic methane-oxidizing activity can induce carbonate precipitation, because the products are bicarbonate and HS-, increasing alkalinity and favoring precipitation of CaCo3 (it is the converse, aerobic sulfide oxidation, that causes release of acid). Heterotrophic activity independent of sulfate reduction can precipitate carbonate by again producing bicarbonate and carbonate ions as well as ammonia, which turns bicarbonate into carbonate -->precipitation of calcium carbonate.
I think a lot of these reactions depend on the buffering capacity of the porewater, which for seawater is quite high. Nevertheless, high rates of non-methanogenic organic matter diagenesis should overwhelm this buffering capacity.
I shouldn't have tried to recall my poor knowledge of carbonate biogeochemistry, which couldn't be rectified by a few Google searches.
"Phosphorite deposits in marine sediments are a long-term sink for an essential nutrient, phosphorus. Here we show that apatite abundance in sediments on the Namibian shelf correlates with the abundance and activity of the giant sulfur bacterium Thiomargarita namibiensis, which suggests that sulfur bacteria drive phosphogenesis. Sediments populated by Thiomargarita showed sharp peaks of pore water phosphate (300 micromolar) and massive phosphorite accumulations (50 grams of phosphorus per kilogram). Laboratory experiments revealed that under anoxic conditions, Thiomargarita released enough phosphate to account for the precipitation of hydroxyapatite observed in the environment."
This is the mechanism of phosphatization I am familiar with, which depends on high rates of organic matter input, which occurs in places like the Namibian shelf. Also in places like the Namibian shelf, you can have such high sedimentation rates and strong currents that turbidites and slumps are common, which is what I thought you were referring to in terms of net negative sedimentation rates.
Whoops, methanogenesis does not involve reducing CO2 with protons, it uses hydrogen (for the H2/CO2 pathway), forgot that- so it would only be acetoclastic (CH3COOH -> CH4+H2O) methanogenesis and anerobic methane oxidation that produce alkalinity and drive CaCO3 pptn. Or something. Whatever.
Leaving aside carbonate pptn/dissolution, perhaps this is what Boesse was talking about low sedimentation rates:
"The observation that CFA is forming authigenically in the FOAM and Mississippi Delta sites is significant, because these sites do not conform to the classic phosphorite depositional environment, which is characterized by eastern boundary current upwelling regimes and low net accumulation rates for terrigenous material relative to biogenic material (Ruttenberg and Berner 1993)."
-but that only means low TERRIGENOUS input.
Anyway, it seems there are reports of non-upwelling-region authigenic phosphate precipitation: see again Ruttenberg and Berner 1993 (who describe phosphorite accumulation in non-upwelling, fairly quickly sedimenting Mississipi delta sediments) and references therein:
"Authigenic precipitation of CFA is known to occur in other environments which differ from the classical upwelling-associated phosphorite formation environment, such as seamounts (BURNETT etal., 1983, and references therein) and the non-upwelling environment of the East Australian continental margin, which is characterized by low sediment accumulation rates and active winnowng and erosion (OâBRIEN et al., 1981,1986,1990; WEGGIE et al., 1990)."
Regardless, the Duoshantuo strata that yielded the putative stem-animals accumulated its phosphorite via the 'classical' pathway now known on upwelling margins. Although perhaps if indeed your standard passive contintental margin accumulates phosphorites, as above ref suggests, such deposits might be more common in the geologic record as compared to the eastern-boundary-current-restricted phosphorites (mediated by filamentous sulfur bacteria phosphate accumulation).
No, HCO3-. But that still changes the pH, even if less efficiently than CO32- would do.
What is alkalinity...?
Makes sense, because this process shifts the equilibrium from CO32- to HCO3-.
Makes sense, because sulfide oxidation turns the strongly basic S2- into the imperceptibly basic SO42-.
A skull from Tusciziphius crispus was recently described from the Miocene/Pliocene of South Carolina. It was privately collected and the family tried to sell it publicly. Fortunately one of the authors of the paper arranged to have it donated to the Natuurhistorisch Museum Rotterdam. The description was published online in a journal called Deinsea in 2008.
Post, K., Lambert, O. & Bianucci, G. 2008. First record of Tusciziphius crispus (Cetacea, Ziphiidae) from the Neogene of the US east coast. Deinsea 12, 1-10.
On the recovery of the specimen, the authors state: "The skull was found by the late Vito Bertucci during 1999 in the Morgan River, Beaufort County, South Carolina, USA, at a location between 32Âº26'50"N, 80Âº35'57"W and 32Âº27'09"N, 80Âº28'44"W. These coordinates and the phosphatised condition of the fossil seem to hint to the 'locally abundant Phosphate Beds' which were mentioned in ancient literature and considered to be of Late Miocene origin (Leidy 1877)." (p. 6).
@David#29- Almost everything you said there is wrong or inaccurate.
Why would you try to speak with authority on something you don't know about? If you don't even know what alkalinity is, then you can't claim to be able to explain any of what I was talking about. (Notice that I said I wasn't 100% sure about my explanation, and gave references).
Thanks for the correcting the order of vowels on Doushantuo, though.
Then please explain.
Because I studied chemistry for a year and had some geochemistry in my paleontology studies?
Perhaps it's just a language barrier. No such term seems to exist in German. Similarly, the terms nitric vs. nitrous and ferric vs. ferrous don't exist in German; we talk, literally, about "nitrogen dioxide", "nitrogen monoxide", "iron(III) oxide" and "iron(II) oxide".
But, hey, the only point we disagree on is whether acid + carbonate gives carbonate (as you said, using the antiquated notation "--" for "2-") or hydrogen carbonate.
I don't really have wish to go chasing down answers on what I consider tangential points, but here is what I would say on a few:
(Carbonate salts dissolve into carbonate ion and counterion, at least initially.)
Sulfide does not exist as S2- in seawater, it exists as HS(-) or H2S. The release of acid I was mentioning occurs because sulfide oxidation makes H2SO4 : sulfuric acid : which subsequently deprotonates to give the ion stable at seawater pH (if indeed it is titrated all the way)- which is sulfate (SO4). Describing H2SO4 as "mildly basic" is not really an informative way to describe it although technically correct.
We also say FeII FeIII or iron(III) or whatever, and I do believe that ferric/ferrous is not an English-only turn of phrase (although it is certainly outdated, it is often used, just like the IUPAC names of chemicals are not always used in place of saying e.g. "ethanol"). However perhaps it was phased out in continental Europe earlier than UK/US, as with metric units.
As for alkalinity: see http://en.wikipedia.org/wiki/Alkalinity
It is certainly a global, key term used in marine geochemistry.
OK, I guess a lot of biology students took a year of inorganic, a year of organic chem. "Geochemistry" is also an extremely wide field, and a lot of diagenetic-related chemistry or biogeochemistry is not widely known even within the field of geochemistry. Even more specific is marine sediment biogeochemistry which I am trying to talk about above. (Seawater has its own specific composition of sulfate, carbonate species, pH, etc.; microbial metabolisms mediating diagenesis in marine sediments are structured stratigraphically due to competition/syntrophic relations, these metabolisms are themselves dependent on rate of organic matter input, which determines the depthwise extent of electron acceptors (such as sulfate) into a redox stratification, which in turn determines which electron accepting activities [metabolisms] occur where; And all these parameters and processes are interdependent- changing one can change others.) I don't know all the answers either, and I was hoping a true geochemist would step in...I have had a course in marine biogeochemistry (some years ago)and I can't even keep it all straight!
I guess I need to break out my notes and really give it some thought if I want an answer, instead of trying to crowdsource or Google my way there..
Oops, I said
I should have said
[from Darren: sorry, was delayed by spam filter]
In neutral water, to the extent they dissolve at all, they dissolve into carbonate ion and counterion, yes. But here we're talking about dissolution due to reaction with an acid: the acid turns the carbonate into hydrogen carbonate (or outright carbonic acid at low pH values), and hydrogen carbonate is, as a rule, better soluble in water than carbonate.
These terms never existed in German. (Part of the larger phenomenon that we don't like making up adjectives as much. For instance, we don't say "sulfuric acid", we literally say "sulfur acid"; nitric and nitrous acid are "saltpeter acid" and "saltpeter-y acid".)
Oh, thanks. The article makes clear the use of this term (which does occur in German!) is restricted to marine geochemistry.
No, I actually was a chemistry student for a year. (Following 4 or 5 years of chemistry olympics, and in total 3 years of ordinary chemistry lessons in highschool.)
would indeed have been inaccurate. That's why I described it as "imperceptibly basic" instead, as you correctly quoted. I'm just too pedantic to write "not basic at all", which would be correct for practical purposes of seawater chemistry.
One doesn't usually refer to the process of producing sulfuric acid as producing a "very mild base", it's understood as producing a strong acid. Calling it a "weak base" is uninformative, since this term is usually reserved for things like bicarbonate, and is so far out of the colloquial usage one can only conclude the speaker misconstrued what they was trying to descibe
I will leave it to you to decide whether you thought you had something meaningful to add to the original posts. On a different note, American students typically take multiple years of chemistry, and BS biology students going for the MCAT take 1 year inorganic, 1 year organic, plus associated labs.
If you could call the study of 71% of the earth's surface, including most of its biomass, most of its organic carbon reservoirs, most of its primary production, etc. etc, "restricted"! I'm pretty sure they also use it in limnology (study of freshwater bodies). It would be better characterized as "restricted" to the geochemistry of water.
I still find this hard to believe (e.g. http://en.wikipedia.org/wiki/Ferrous). What is sulfite in German? Nitrate? Nitrite?
AD: Have you thought you had something meaningful to add? You know, beyond "oho, you sooo wrong"?
@Victor: Welp, I knew it would sound like that if I responded to David's points. But see what I wrote before the last post.
When one posts open-ended musings, with scholarly references, and admitting it isn't all correct, it's sort of irritating to have as responses "Oh, the answer is obviously X simple high-school level chemistry principle" and be (incorrectly) informed you are wrong on some basic point.
But I suppose one shouldn't try to make points of principle or etiquette on the internet, it never looks good and is only different by degree from the material that ends up on eg Encyclopedia Dramatica...