Alkenone Paleotemperature Determinations

The organic biomarker proxy for past sea surface temperatures ("U37k") came to paleoceanography from an unexpected direction. Nearly all paleoceanographic tools rely on some aspect of the fossilized hard parts of marine organisms. Thus, assemblages of calcareous microplankton such as foraminifera and coccoliths, or of siliceous plankton such as radiolaria and diatoms, provided the basis for the CLIMAP reconstruction of the Ice Age ocean (CLIMAP, 1976, 1981). Additionally, a host of chemical methods relies on the same hard parts to furnish isotopic and trace element signatures, and generally requires that skeletal material be well preserved. The alkenone method differs in several important ways. Individual molecules, extracted and separated from a matrix of hundreds to thousands of other organic compounds, are the targets. In most cases, the remnant alkenones and alkenoates that are the subject of this review constitute no more, and often considerably less, than a few percent of their initial flux that left the surface layer of the ocean and fell toward the sediments. Good preservation is thus not a major issue for use of the proxy. In addition, while many geochemical techniques assume that skeletal material is a passive recorder of isotopic and trace element composition of seawater, and that incorporation of paleo-environmental signals follows thermodynamic laws that can be modeled using nonbiogenic phases in the laboratory, the alkenone method assumes that the ratios of biomarkers measured were actively regulated by the producing organisms in life according to the temperature of the water in which they grew.Alkenone paleothermometry promises a direct estimate of near-surface ocean temperatures. Alkenones and the related alkenoates come exclusively from a few species of haptophyte algae. These organisms require sunlight, and they generally prefer the upper photic zone. The environmental information contained in their molecular fossils therefore is quite specific, although, as will be discussed at length in a later section, ambiguities still exist on the depth and seasonal variations of alkenone-producing species in the ocean. In contrast, many assemblages of planktonic organisms such as foraminifera and radiolaria contain many species known to live well below the surface mixed layer. The link between microfossil assemblages and sea surface temperature and salinity is therefore indirect and statistical, rather than mechanistic.As originally defined by the Bristol organic geochemistry group (Brassell, 1986a, b), the U37k index reflected the proportions of the di-(C37:2), tri-(C37:3), and tetra-(C37:4) unsaturated ketones. Subsequent work showed that there was no empirical benefit to including the C37:4 ketone in a paleotemperature equation. The currently accepted U37k' index (Prahl and Wakeham, 1987) varies positively with temperature, and is defined as C37:2/(C37:2+C37:3), where C37:2 represents the quantity of the di-unsaturated ketone and C37:3 the quantity of the tri-unsaturated form. The alkenone paleotemperature proxy thus depends only on the relative proportions of the common C37 ketones and not on their absolute amounts. Furthermore, although the alkenones are produced by calcareous algae, they survive in sediments where carbonate has dissolved, as first recognized by Marlowe et al. (1984a, b) and Brassell et al. (1986a). The above expression for the index shows that it can vary between 0 and 1.0; thus, it may saturate at either extremely cold or warm temperatures.Alkenones appear recalcitrant to diagenesis in the water column and within sediments relative to other large macromolecules. Indeed, the first reported occurrence of alkenones came not from recent material, but from Miocene age sediments of the Walvis Ridge (Boon et al., 1978). Shortly thereafter, these compounds were linked to modern haptophyte algae, principally Emiliania huxleyi (de Leeuw et al., 1980; Volkman et al., 1980a, b; Marlowe et al., 1984a, b). Reviews of lipid analyses of Deep Sea Drilling Project sediments revealed that most sediments of Pleistocene through mid-Eocene age appeared to contain measurable quantities of alkenones and alkenoates ( Marlowe et al., 1984a, 1990; Brassell, 1993). Brassell et al. (1986a) provided the seminal study linking alkenone unsaturation to paleotemperature fluctuations in the Late Pleistocene. After noting that modern surface sediments differed in their unsaturation ratios depending on latitude, Brassell et al. (1986a, b) reconstructed alkenone unsaturation in conjunction with benthic and planktonic foraminiferal δ18O over the last 8×105 yr in a core from the subtropical North Atlantic. The unsaturation index declined during glacial periods, suggesting cooler surface ocean temperatures during ice age conditions. The authors further demonstrated that the alkenone index gave a continuous paleoclimatic curve, even in intervals barren of foraminifera due to dissolution. Prahl and Wakeham (1987) and Prahl et al. (1988) proposed the first quantitative calibration of alkenone unsaturation to growth temperature. Unsaturation parameters measured on a strain of E.huxleyi grown in the laboratory at known temperatures were compared to the unsaturation index on particulate material collected from the near-surface ocean in the northeast Pacific. Prahl and Wakeham (1987) showed that the laboratory calibration appeared to apply well to the field observations of unsaturation and the water temperature in which the alkenones apparently were synthesized. The calibration of alkenone unsaturation to temperatures expanded with the first systematic study of core-top sediments by Sikes et al. (1991). That study produced two important results: (i) the unsaturation index in recent sediments followed a relation to overlying sea surface temperatures (SSTs) very similar to the Prahl et al. (1988) calibration, and (ii) there appeared to be no ill effects on the unsaturation index over the time of core storage. Pristine or frozen samples were therefore not needed to produce good estimates of the U37k' index for paleoceanographic studies.As with any paleoceanographic proxy, a number of uncertainties must be evaluated that could affect the accuracy measurement as an estimate of past SSTs. The principal caveats raised can be broadly categorized as ecological, physiological, genetic, and diagenetic. All describe factors, which could cause the U37k' index to deviate from a unique relation to SSTs. Ecological concerns come from observations that alkenone-producing species do not inhabit precisely the same depth throughout the ocean, and that they vary in abundance seasonally. The alkenone unsaturation parameter recorded by sediments could therefore measure past temperatures very precisely, but at which depths, and with what seasonal bias? It is also possible that the proportions of alkenones synthesized by haptophyte algae vary with growth rate, independent of temperature. Our present state of ignorance dictates that we do not know the growth phase of haptophyte material exported out of the photic zone - whether the products represent the initial exponential growth phase observed in culture or stationary growth. Natural populations also differ in their genetic composition. Alkenone-producing species are notable for their wide range of environmental tolerances. The consequences for the U37k' index of genetic variations within strains of the same producing species and between the different alkenone-synthesizing species are still debated. In addition, alkenones measured in sediments represent the surviving molecules of a series of degradational pathways that begin in the water column, proceed to the sediment/water interface, and may continue into the sediment. Should there be a bias in the relative lability of the C37:2 and C37:3 ketones, this would be imparted to paleoceanographic reconstructions of temperature.As should become clear, the U37k' index appears nevertheless to provide a remarkably faithful estimate of paleotemperatures near the sea surface. At the same time, difficulties in matching the space and timescales of modern process studies to the information contained in sediments mean that the caveats raised above remain significant. Field studies provide only snapshots of haptophyte abundance and alkenone unsaturation parameters, sediment traps provide only a few years of data at only a few locations in the global ocean, and it is unclear how well laboratory cultures replicate the natural environment. I have endeavored to treat different lines of evidence systematically, but I have found it difficult to discuss each aspect in a purely serial way. The reader will therefore be asked to digest a review in which very diverse measurements and paradigms are woven together to answer the central question of how to reconstruct past ocean surface temperatures with the U37k' proxy.