Matthew D. McCarthy

The Pliocene Paradox (Mechanisms for a Permanent El Niño)

During the early Pliocene, 5 to 3 million years ago, globally averaged temperatures were substantially higher than they are today, even though the external factors that determine climate were essentially the same. In the tropics, El Niño was continual (or “permanent”) rather than intermittent. The appearance of northern continental glaciers, and of cold surface waters in oceanic upwelling zones in low latitudes (both coastal and equatorial), signaled the termination of those warm climate conditions and the end of permanent El Niño. This led to the amplification of obliquity (but not precession) cycles in equatorial sea surface temperatures and in global ice volume, with the former leading the latter by several thousand years. A possible explanation is that the gradual shoaling of the oceanic thermocline reached a threshold around 3 million years ago, when the winds started bringing cold waters to the surface in low latitudes. This introduced feedbacks involving ocean-atmosphere interactions that, along with ice-albedo feedbacks, amplified obliquity cycles. A future melting of glaciers, changes in the hydrological cycle, and a deepening of the thermocline could restore the warm conditions of the early Pliocene.

A review of nitrogen isotopic alteration in marine sediments

Key Points: Use of sedimentary nitrogen isotopes is examined; On average, sediment 15N/14N increases approx. 2 per mil during early burial; Isotopic alteration scales with water depth Abstract: Nitrogen isotopes are an important tool for evaluating past biogeochemical cycling from the paleoceanographic record. However, bulk sedimentary nitrogen isotope ratios, which can be determined routinely and at minimal cost, may be altered during burial and early sedimentary diagenesis, particularly outside of continental margin settings. The causes and detailed mechanisms of isotopic alteration are still under investigation. Case studies of the Mediterranean and South China Seas underscore the complexities of investigating isotopic alteration. In an effort to evaluate the evidence for alteration of the sedimentary N isotopic signal and try to quantify the net effect, we have compiled and compared data demonstrating alteration from the published literature. A >100 point comparison of sediment trap and surface sedimentary nitrogen isotope values demonstrates that, at sites located off of the continental margins, an increase in sediment 15N/14N occurs during early burial, likely at the seafloor. The extent of isotopic alteration appears to be a function of water depth. Depth-related differences in oxygen exposure time at the seafloor are likely the dominant control on the extent of N isotopic alteration. Moreover, the compiled data suggest that the degree of alteration is likely to be uniform through time at most sites so that bulk sedimentary isotope records likely provide a good means for evaluating relative changes in the global N cycle.

Evidence for El Niño–like conditions during the Pliocene

The modern tropical Pacific Ocean is characterized by strong east-west asymmetry in sea surface temperature and subsurface thermocline depth coupled to easterly trade winds and zonal atmospheric, or Walker, circulation. Walker circulation and the “normal” east-west asymmetry of sea surface temperature and thermocline depth break down temporarily during El Niño events. Since these temporary deviations from the “normal” tropical climate state are known to have global impacts, it is important to consider whether permanent shifts in the mean tropical Pacific climate state are an integral part of global climate change on longer time scales. To understand the link between tropical conditions and global warmth, we focus our study on the early Pliocene, the most recent period in Earth’s history of sustained global warmth relative to today. A data synthesis of tropical paleoceanographic data, including a new alkenone unsaturation index ( U 37 )–based sea surface temperature record from the eastern equatorial Pacific, indicates that, in the early Pliocene, the east-west asymmetry in sea surface temperature and thermocline depth was reduced compared to today and the tropical Pacific was in a permanent El Niño–like state. Thus, the “normal” mean state of the modern tropical Pacific is not a persistent feature of Earth’s climate over long time scales. INTRODUCTION Studies of the el niño Southern Oscillation (enSO) phenomenon indicate that, through atmospheric teleconnections, small changes in the pattern of tropical Pacific sea surface temperature (SSt) have a global impact on interannual time scales (Alexander et al., 2002). Although the mechanisms responsible for the enSO do not directly apply to studies of climate changes on longer time scales, enSO events provide a clear example of how changes in the distribution of SSt across the Pacific Ocean can have far-field climate effects such as higher than average rainfall in the southwestern United States and higher than average temperature in temperate regions of north America. the potential global effect of small, long-term changes in the tropical SSt pattern is substantiated by modeling studies (Yin and Battisti, 2001; Barreiro et al., 2005). However, while the impact of changes in the mean SSt pattern of the tropical Pacific on global climate is recognized, the circumstances under which they could occur are difficult to predict. For example, in simulations of future climate change forced with enhanced greenhouse gases, climate models do not give consistent results in the tropical Pacific: some predict no long-term changes; some predict el niño–like mean conditions; still others predict la niña–like mean conditions (cane, 2005; collins, 2005). Because the instrumental record is too short to examine multidecadal and longer-term climate changes, paleoceanographic studies are needed to establish whether modern mean tropical SSt patterns across tropical basins are stable over long time periods. these data-based studies can then be used to test and improve theoretical and computer models of long-term climate change, including those that are used to predict future climate change. While much can be learned from studying the extreme globally cool climate of the last Glacial Maximum (lGM), it is also important to focus on past periods of global warmth prior to the ice ages of the past few million years. Paleoceanographic studies generally indicate that the mean SSt of the Pacific tropical ocean was stable within a few degrees over millions of years, yet these studies rarely include enough data to characterize the east-west SSt difference across the Pacific. For example, the Pliocene warm period (ca. 4.5–3.0 Ma) (Fig. 1) has been the focus of much interest among paleoclimatologists because of the need to understand climate processes in past times of global warmth. landmark studies, such as those by the Pliocene research, interpretation, and Synoptic Mapping (PriSM) group, including compilations of oceanic and terrestrial data (Dowsett et al., 1996, 2005; thompson and Fleming, 1996) and modeling studies (Haywood et al., 2000; Sloan et al., 1996), indicate that the Pliocene was significantly warmer than today, especially in extratropical regions. However, the PriSM reconstructions include very little data from the tropical Pacific Ocean and therefore do not provide insight into changes in tropical SSt patterns. crowley (1996) pointed out the urgent need for more tropical data in order to further constrain the mechanisms that explain global climate conditions in the Pliocene, and in the last decade, several studies were conducted that focus on the tropical Pacific utilizing Pliocene-age material obtained by the Ocean Drilling Program.

Nutrient regime shift in the western North Atlantic indicated by compound-specific δ15N of deep-sea gorgonian corals

Despite the importance of the nitrogen (N) cycle on marine productivity, little is known about variability in N sources and cycling in the ocean in relation to natural and anthropogenic climate change. Beyond the last few decades of scientific observation, knowledge depends largely on proxy records derived from nitrogen stable isotopes (δ15N) preserved in sediments and other bioarchives. Traditional bulk δ15N measurements, however, represent the combined influence of N source and subsequent trophic transfers, often confounding environmental interpretation. Recently, compound-specific analysis of individual amino acids (δ15N-AA) has been shown as a means to deconvolve trophic level versus N source effects on the δ15N variability of bulk organic matter. Here, we demonstrate the first use of δ15N-AA in a paleoceanographic study, through analysis of annually secreted growth rings preserved in the organic endoskeletons of deep-sea gorgonian corals. In the Northwest Atlantic off Nova Scotia, coral δ15N is correlated with increasing presence of subtropical versus subpolar slope waters over the twentieth century. By using the new δ15N-AA approach to control for variable trophic processing, we are able to interpret coral bulk δ15N values as a proxy for nitrate source and, hence, slope water source partitioning. We conclude that the persistence of the warm, nutrient-rich regime since the early 1970s is largely unique in the context of the last approximately 1,800 yr. This evidence suggests that nutrient variability in this region is coordinated with recent changes in global climate and underscores the broad potential of δ15N-AA for paleoceanographic studies of the marine N cycle.

A 5 million year comparison of Mg/Ca and alkenone paleothermometers

Geochemical sea surface temperature (SST) proxies such as the magnesium to calcium ratio (Mg/Ca) in foraminifera and the alkenone unsaturation index (UK′37) are becoming widely used in pre-Pleistocene climate records. This study quantitatively compares previously published Mg/Ca and UK′37 data from Ocean Drilling Program (ODP) site 847 in the eastern equatorial Pacific to assess the utility of these proxies to reconstruct tropical SST over the last 5 Ma. Foraminiferal Mg/Ca–SST calibrations that include a dissolution correction are most appropriate at this location because they provide SST estimates for the youngest sample that are close to modern mean annual SST. The long-term trends in the two records are remarkably similar and confirm a ∼3.5°C cooling trend from the early Pliocene warm period to the late Pleistocene noted in previous work. Absolute temperature estimates are similar for both proxies when errors in the dissolution correction used to estimate SST from Mg/Ca are taken into account. Comparing the two SST records at ODP site 847 to other records in the region shows that the eastern equatorial Pacific was 2–4°C warmer during the early Pliocene compared to today.

Tracing Carbon Sources through Aquatic and Terrestrial Food Webs Using Amino Acid Stable Isotope Fingerprinting

Tracing the origin of nutrients is a fundamental goal of food web research but methodological issues associated with current research techniques such as using stable isotope ratios of bulk tissue can lead to confounding results. We investigated whether naturally occurring δ13C patterns among amino acids (δ13CAA) could distinguish between multiple aquatic and terrestrial primary production sources. We found that δ13CAA patterns in contrast to bulk δ13C values distinguished between carbon derived from algae, seagrass, terrestrial plants, bacteria and fungi. Furthermore, we showed for two aquatic producers that their δ13CAA patterns were largely unaffected by different environmental conditions despite substantial shifts in bulk δ13C values. The potential of assessing the major carbon sources at the base of the food web was demonstrated for freshwater, pelagic, and estuarine consumers; consumer δ13C patterns of essential amino acids largely matched those of the dominant primary producers in each system. Since amino acids make up about half of organismal carbon, source diagnostic isotope fingerprints can be used as a new complementary approach to overcome some of the limitations of variable source bulk isotope values commonly encountered in estuarine areas and other complex environments with mixed aquatic and terrestrial inputs.

Increasing subtropical North Pacific Ocean nitrogen fixation since the Little Ice Age

The North Pacific subtropical gyre (NPSG) plays a major part in the export of carbon and other nutrients to the deep ocean. Primary production in the NPSG has increased in recent decades despite a reduction in nutrient supply to surface waters. It is thought that this apparent paradox can be explained by a shift in plankton community structure from mostly eukaryotes to mostly nitrogen-fixing prokaryotes. It remains uncertain, however, whether the plankton community domain shift can be linked to cyclical climate variability or a long-term global warming trend. Here we analyse records of bulk and amino-acid-specific 15N/14N isotopic ratios (δ15N) preserved in the skeletons of long-lived deep-sea proteinaceous corals collected from the Hawaiian archipelago; these isotopic records serve as a proxy for the source of nitrogen-supported export production through time. We find that the recent increase in nitrogen fixation is the continuation of a much larger, centennial-scale trend. After a millennium of relatively minor fluctuation, δ15N decreases between 1850 and the present. The total shift in δ15N of −2 per mil over this period is comparable to the total change in global mean sedimentary δ15N across the Pleistocene–Holocene transition, but it is happening an order of magnitude faster. We use a steady-state model and find that the isotopic mass balance between nitrate and nitrogen fixation implies a 17 to 27 per cent increase in nitrogen fixation over this time period. A comparison with independent records suggests that the increase in nitrogen fixation might be linked to Northern Hemisphere climate change since the end of the Little Ice Age.

Carbon and nitrogen isotope fractionation of amino acids in an avian marine predator, the gentoo penguin (Pygoscelis papua)

Compound-specific stable isotope analysis (CSIA) of amino acids (AA) has rapidly become a powerful tool in studies of food web architecture, resource use, and biogeochemical cycling. However, applications to avian ecology have been limited because no controlled studies have examined the patterns in AA isotope fractionation in birds. We conducted a controlled CSIA feeding experiment on an avian species, the gentoo penguin (Pygoscelis papua), to examine patterns in individual AA carbon and nitrogen stable isotope fractionation between diet (D) and consumer (C) (Δ13CC-D and Δ15NC-D, respectively). We found that essential AA δ13C values and source AA δ15N values in feathers showed minimal trophic fractionation between diet and consumer, providing independent but complimentary archival proxies for primary producers and nitrogen sources respectively, at the base of food webs supporting penguins. Variations in nonessential AA Δ13CC-D values reflected differences in macromolecule sources used for biosynthesis (e.g., protein vs. lipids) and provided a metric to assess resource utilization. The avian-specific nitrogen trophic discrimination factor (TDFGlu-Phe = 3.5 ± 0.4‰) that we calculated from the difference in trophic fractionation (Δ15NC-D) of glutamic acid and phenylalanine was significantly lower than the conventional literature value of 7.6‰. Trophic positions of five species of wild penguins calculated using a multi-TDFGlu-Phe equation with the avian-specific TDFGlu-Phe value from our experiment provided estimates that were more ecologically realistic than estimates using a single TDFGlu-Phe of 7.6‰ from the previous literature. Our results provide a quantitative, mechanistic framework for the use of CSIA in nonlethal, archival feathers to study the movement and foraging ecology of avian consumers.

Range Expansion of the Jumbo Squid in the NE Pacific: δ15N Decrypts Multiple Origins, Migration and Habitat Use

Coincident with climate shifts and anthropogenic perturbations, the highly voracious jumbo squid Dosidicus gigas reached unprecedented northern latitudes along the NE Pacific margin post 1997–98. The physical or biological drivers of this expansion, as well as its ecological consequences remain unknown. Here, novel analysis from both bulk tissues and individual amino acids (Phenylalanine; Phe and Glutamic acid; Glu) in both gladii and muscle of D. gigas captured in the Northern California Current System (NCCS) documents for the first time multiple geographic origins and migration. Phe δ15N values, a proxy for habitat baseline δ15N values, confirm at least three different geographic origins that were initially detected by highly variable bulk δ15N values in gladii for squid at small sizes (<30 cm gladii length). In contrast, bulk δ15N values from gladii of large squid (>60 cm) converged, indicating feeding in a common ecosystem. The strong latitudinal gradient in Phe δ15N values from composite muscle samples further confirmed residency at a point in time for large squid in the NCCS. These results contrast with previous ideas, and indicate that small squid are highly migratory, move into the NCCS from two or more distinct geographic origins, and use this ecosystem mainly for feeding. These results represent the first direct information on the origins, immigration and habitat use of this key “invasive” predator in the NCCS, with wide implications for understanding both the mechanisms of periodic D. gigas population range expansions, and effects on ecosystem trophic structure.

Compound-specific δ15N amino acid measurements in littoral mussels in the California upwelling ecosystem: a new approach to generating baseline δ15N Isoscapes for coastal ecosystems.

We explored δ15N compound-specific amino acid isotope data (CSI-AA) in filter-feeding intertidal mussels (Mytilus californianus) as a new approach to construct integrated isoscapes of coastal primary production. We examined spatial δ15N gradients in the California Upwelling Ecosystem (CUE), determining bulk δ15N values of mussel tissue from 28 sites between Port Orford, Oregon and La Jolla, California, and applying CSI-AA at selected sites to decouple trophic effects from isotopic values at the base of the food web. Bulk δ15N values showed a strong linear trend with latitude, increasing from North to South (from ∼7‰ to ∼12‰, R2 = 0.759). In contrast, CSI-AA trophic position estimates showed no correlation with latitude. The δ15N trend is therefore most consistent with a baseline δ15N gradient, likely due to the mixing of two source waters: low δ15N nitrate from the southward flowing surface California Current, and the northward transport of the California Undercurrent (CUC), with15N-enriched nitrate. This interpretation is strongly supported by a similar linear gradient in δ15N values of phenylalanine (δ15NPhe), the best AA proxy for baseline δ15N values. We hypothesize δ15NPhe values in intertidal mussels can approximate annual integrated δ15N values of coastal phytoplankton primary production. We therefore used δ15NPhe values to generate the first compound-specific nitrogen isoscape for the coastal Northeast Pacific, which indicates a remarkably linear gradient in coastal primary production δ15N values. We propose that δ15NPhe isoscapes derived from filter feeders can directly characterize baseline δ15N values across major biochemical provinces, with potential applications for understanding migratory and feeding patterns of top predators, monitoring effects of climate change, and study of paleo- archives.