BREVIA

a clade. Mineralization of most animal skeletons is

biologically controlled, occurring in an environment

Seawater Chemistry and Early isolated from seawater (9). As a result, seawater
chemistry does not have a direct influence on the
mineralogy of most animal skeletons the way it does
Carbonate Biomineralization for biomineralizers that induce mineralization direct-
ly from seawater (9). However, seawater chemistry
Susannah M. Porter may have played an indirect role in determining
rganisms use a wide variety of minerals to have been aragonitic, and 10 are highly likely to skeletal mineralogy by affecting the physiological

O make their skeletons, including silica, ap- have been calcitic (either high- or low-magnesium
atite, and several polymorphs of carbon- calcite). Mapping inferred skeletal mineralogies on
ate, in particular aragonite and calcite. It is unclear, first appearances of mineralization (FAMs) results
costs of biomineralization (1). Experimental and
paleontological evidence suggests organisms have
greater difficulty producing skeletons not favored
however, why different taxa evolved to use one in a striking pattern (Fig. 1A): Aragonitic taxa sys- by seawater chemistry (2, 10); thus, it is reasonable
mineral rather than another. Lineages rarely tematically appeared earlier, with FAMs occuring to posit that, when skeletons first evolved, natural
switched their mineralogy after acquiring skeletons, in the Ediacaran Period from Nemakit-Daldynian selection favored the mineral easiest to precipitate
suggesting that, for most taxa, ambient seawater Stage followed by calcitic taxa, which began min- (1). Once selected, however, taxa rarely switched
chemistry does not strongly influence skeletal min- eralizing in the Tommotian Stage or later. mineralogies even though they may have been

Downloaded from www.sciencemag.org on October 12, 2012

eralogy (1). However, seawater negatively affected when
chemistry may have dictated Mg2+/Ca2+ ratios changed (2).
the choice of skeletal min- Although initially optimal,
eralogy at the time skeletons skeletal mineralogy may since
first evolved in a clade (1, 2). have presented a considerable
This hypothesis was tested evolutionary constraint.
by assessing the ancestral min-
References and Notes
eralogy (aragonite versus cal- 1. A. H. Knoll, Rev. Mineral.
cite) of 21 metazoan taxa that Geochem. 54, 329 (2003).
evolved mineralization during 2. S. M. Stanley, L. A. Hardie,
the late Ediacaran through the Palaeogeogr. Palaeoclimatol.
Palaeoecol. 144, 3 (1998).
Ordovician (~550 to 444 mil- 3. S. Bengtson, S. Conway Morris,
lion years ago) and comparing in Origin and Early Evolution of
the resulting pattern with inde- the Metazoa, J. H. Lipps,
P. W. Signor, Eds. (Plenum,
pendent constraints on coeval
New York, 1992), pp. 447481.
seawater chemistry (Fig. 1 and 4. T. K. Lowenstein, M. N. Timofeeff,
tables S1 and S2). Each taxon is S. T. Brennan, L. A. Hardie,
thought to represent an inde- R. V. Demicco, Science 294, 1086
(2001).
pendent acquisition of biomin- 5. J. W. Morse, Q. Wang, M. Y. Tsio,
eralization (3) and therefore Fig. 1. First appearances of carbonate skeletons in animals (A) and constraints on seawater Geology 25, 85 (1997).
should offer an independent chemistry (B) during the Ediacaran through the Ordovician Periods. Fluid inclusion data are listed in 6. S. T. Brennan, T. K. Lowenstein,
J. Horita, Geology 32, 473 (2004).
test of the hypothesis. Alterna- table S2. Indirect evidence for seawater chemistry, reviewed in (2), refers to constraints from 7. O. Petrychenko, T. Peryt,
tive taxonomic interpretations nonskeletal marine precipitates and from models of mid-ocean ridge hydrothermal brine fluxes. E. Chechel, Chem. Geol. 219,
(table S1) affect the degree of Because most taxa are fossilized in abundance, it is assumed that first appearances of skeletons in 149 (2005).
support for the pattern presented the fossil record closely approximate actual first appearances of skeletons. Calcite sea and 8. V. M. Kovalevych, T. M. Peryt,
here but do not change it. Four aragonite sea refer to seawater that favors calcite and aragonite precipitation, respectively.
W. Zang, S. V. Vovnyuk, Terra
Nova 18, 95 (2006).
taxa known to be polyphyletic Boundary age constraints are from the International Commission on Stratigraphy International 9. S. Weiner, P. M. Dove, Rev.
were excluded (table S1). Stratigraphic Chart (2007) (www.stratigraphy.org/cheu.pdf) and (11). Although there is uncertainty Mineral. Geochem. 54, 1 (2003).
Determining the primary regarding the position of stage boundaries relative to some first appearances of skeletons, the 10. J. B. Ries, Paleobiology 31,
445 (2005).
mineralogy of ancient carbon- sequence of taxa is unaffected (table S2). Ma, million years; T, Tommotian Stage; A, Atdabanian 11. A. C. Maloof, D. P. Schrag,
ate fossils is not straightforward Stage; Bot/Toy, Botomian and Toyonian Stages. J. L. Crowley, S. A. Bowring, Can.
because aragonite recrystallizes to calcite at Earths Fluid inclusions in marine evaporite deposits J. Earth Sci. 42, 2195 (2005).
12. This work benefited from discussions with S. Awramik,
surface pressures. As a result, formerly aragonitic provide the most definitive constraints on the P. Baker, J. Boles, S. Carlson, J. Grotzinger, J. Kellogg,
skeletons are often preserved as calcite. Five well- Mg2+/Ca2+ ratio of ancient seawater (4), which A. Knoll, T. Lowenstein, A. Maloof, J. Payne, J. Sorauf,
accepted criteria were used to infer primary min- is thought to be the primary control on marine F. Spera, M. Vendrasco, J. Weaver, S. Weiner, and
eralogy [Supporting Online Material (SOM) nonskeletal carbonate mineralogy (2, 5). These B. Zempolich. Three anonymous reviewers offered helpful
comments on earlier drafts. Supported by NASA grant no.
text]: (i) presence of original aragonite, (ii) phylo- indicate that the Mg2+/Ca2+ ratio of late Ediacaran
EXB04-0000-0117.
genetic distribution of mineralogies in extant mem- seawater favored aragonite precipitation (4, 6),
2+ 2+ Supporting Online Material
bers of a group, (iii) quality of preservation of original whereas the Mg /Ca ratio of Tommotian/ www.sciencemag.org/cgi/content/full/316/5829/1302/DC1
microstructures in calcite, (iv) morphology of crys- Atdabanian through Toyonian seawater (4, 6, 7), SOM Text
tals replicated by secondary minerals, and (v) mag- as well as that of late Ordovician seawater (4, 8), Tables S1 and S2
nesium content. Evidence for primary mineralogy favored calcite precipitation (Fig. 1B and table S2). References
was drawn from the literature (table S1) and crit- The close correspondence between the pattern 7 November 2006; accepted 27 February 2007
ically evaluated with respect to these criteria. of FAMs and the constraints on seawater chemis- 10.1126/science.1137284
For 18 of the 21 taxa, primary mineralogy is try (Fig. 1) suggests that selection of aragonite versus Department of Earth Science, University of California at
known with at least some confidence. Of these, calcite was largely dictated by seawater chemistry at Santa Barbara, Santa Barbara, CA 93106, USA. E-mail:
eight are highly likely (N = 4) or likely (N = 4) to the time mineralized skeletons were first acquired in porter@geol.ucsb.edu

1302 1 JUNE 2007 VOL 316 SCIENCE www.sciencemag.org