George E. A. Swann

North Pacific seasonality and the glaciation of North America 2.7 million years ago

In the context of gradual Cenozoic cooling, the timing of the onset of significant Northern Hemisphere glaciation 2.7 million years ago is consistent with Milankovitchs orbital theory, which posited that ice sheets grow when polar summertime insolation and temperature are low. However, the role of moisture supply in the initiation of large Northern Hemisphere ice sheets has remained unclear. The subarctic Pacific Ocean represents a significant source of water vapour to boreal North America, but it has been largely overlooked in efforts to explain Northern Hemisphere glaciation. Here we present alkenone unsaturation ratios and diatom oxygen isotope ratios from a sediment core in the western subarctic Pacific Ocean, indicating that 2.7 million years ago late-summer sea surface temperatures in this ocean region rose in response to an increase in stratification. At the same time, winter sea surface temperatures cooled, winter floating ice became more abundant and global climate descended into glacial conditions. We suggest that the observed summer warming extended into the autumn, providing water vapour to northern North America, where it precipitated and accumulated as snow, and thus allowed the initiation of Northern Hemisphere glaciation.

Diatom δ18O evidence for the development of the modern halocline system in the subarctic northwest Pacific at the onset of major Northern Hemisphere glaciation

Establishing a time frame for the development of the modern halocline and stratified water column in the subarctic North Pacific has significant paleoclimatic implications. Here we present a d18O(diatom) record consisting of only two species that represents autumn/winter conditions in the region across the onset of major Northern Hemisphere glaciation boundary. At circa 2.73 Ma a decrease in d18O(diatom) of 4.6% occurs, whereas previously published d18O(foram) results show a 2.6% increase. The d18O(diatom) and Uk37 sea surface reconstructions indicate both a significant freshening of 2–4 practical salinity units and an increase in surface temperatures in the summer to early winter period from circa 2.73 Ma onward. In contrast, the concomitant increase in d18O(foram) is likely to be reflective of conditions beneath the mesothermal structure and/or spring conditions when warmer sea surface temperatures are not present in the region. These results are consistent with the development of the modern halocline system at 2.73 Ma with year-round stratification of the water column and a strengthened seasonal thermocline during the summer to early winter period, resulting in one of the largest summer to winter temperature gradients in the open ocean. The onset of stratification would also have led to a warm pool of surface water from circa 2.73 Ma, which may have provided a potential source of extra moisture needed to supply the growing North American ice sheets at this time.

ISOTOPES IN MARINE SEDIMENTS

Marine sediments provide long continuous records of past climate changes at intraannual, annual to centennial scale resolutions enabling insights into past changes within both oceanic and continental environments. Stable isotopes provide palaeoceanographers with the means to reconstruct a range of variables including surface and deep ocean circulation patterns, sea surface and bottom water temperature, sea surface salinity, iceberg activity and origin, upwelling intensity, productivity, nutrient utilisation, surface-water dissolved carbon dioxide content and water-column oxygen content in addition to inferences on global ice volume, ice sheet failure, river discharge, aridity, vegetation composition, and continental erosion rates. The fundamental source of stable isotope information derived from marine sediment archives primarily originates from oxygen and carbon. Comprehensive introductions on oxygen and carbon isotopes and their physico-chemical behaviour/systematics are given in Craig and Gordon (1965), Garlick (1974), Hoefs (1997), Criss (1999), Rohling and Cooke (1999) and Zeebe and Wolf-Gladrow (2001). This chapter describes the current state of palaeoceanographic and palaeoclimatic uses of both oxygen and carbon isotopes, alongside less frequently applied stable isotopes such as nitrogen, silicon and boron.

Diatom oxygen isotopes : evidence of a species effect in the sediment record

Diatom oxygen isotope measurements are commonly made on bulk mixed species assemblages due to the difficulty in purifying and separating individual taxa. As such, it is essential to understand processes in diatoms which may lead to isotope offsets both between and within individual species. Existing studies have suggested that mechanisms which may lead to isotopes offset in diatoms, such as vital effects, are either nonexistent or negligible. Here, we present a suite of diatom oxygen isotope data from the onset of major Northern Hemisphere Glaciation at ODP site 882 in the northwest Pacific Ocean which display large offsets ( mean = 1.23 parts per thousand, max = 3.51 parts per thousand, error = 0.84 parts per thousand) between two different size fractions ( 75 - 150 mu m and > 150 mu m) that are dominated by only two species: Coscinodiscus marginatus and Coscinodiscus radiatus. These offsets are most likely size related, although additional interspecies and intraspecies effects may also be important in determining the exact magnitude of the offsets. Consequently, considerable care is needed when interpreting bulk diatom oxygen isotope data in relation to paleoenvironmental change, especially when the amount of stratigraphical change within the isotopes is small.

A highly productive Subarctic Atlantic during the Last Interglacial and the role of diatoms

The Last Interglacial (LIG), corresponding to Marine Isotope Stage (MIS) 5e, provides a reference of interglacial climate variability in the absence of anthropogenic forcing. Using an expanded section of the LIG gained at Integrated Ocean Drilling Program Site U1304 in the Subarctic Atlantic, we demonstrate that the early MIS 5e was marked by oceanographic conditions conducive for high diatom production and accumulation. The appearance of diatom-dominated laminated oozes ∼3 k.y. after the beginning of MIS 5e at ca. 125 ka coincides with a shift to higher δ 30 Si diat values together with the dominance of Thalassiothrix longissima , indicative of increased nutrient availability and silicic acid utilization in surface waters. Though the Subarctic Front provided the physical conditions for high diatom production and deposition, these processes alone are insufficient to explain the high rates of siliceous productivity and the formation of diatomaceous sediments. Instead, the additional presence of an increased nutrient pool provided by Subantarctic Mode Water played the decisive role in initiating and sustaining diatom production. The high diatom productivity and the occurrence of diatomaceous sediments in the late Quaternary challenge the current hypothesis of a silica-depleted North Atlantic during the LIG.

Constraining modern‐day silicon cycling in Lake Baikal

Constraining the continental silicon cycle is a key requirement in attempts to understand both nutrient fluxes to the ocean and linkages between silicon and carbon cycling over different time scales. Silicon isotope data of dissolved silica (δ30SiDSi) are presented here from Lake Baikal and its catchment in central Siberia. As well as being the worlds oldest and voluminous lake, Lake Baikal lies within the seventh largest drainage basin in the world and exports significant amounts of freshwater into the Arctic Ocean. Data from river waters accounting for ~92% of annual river inflow to the lake suggest no seasonal alteration or anthropogenic impact on river δ30SiDSi composition. The absence of a change in δ30SiDSi within the Selenga Delta, through which 62% of riverine flow passes, suggests a net balance between biogenic uptake and dissolution in this system. A key feature of this study is the use of δ30SiDSi to examine seasonal and spatial variations in DSi utilization and export across the lake. Using an open system model against deepwater δ30SiDSi values from the lake, we estimate that 20–24% of DSi entering Lake Baikal is exported into the sediment record. While highlighting the impact that lakes may have upon the sequestration of continental DSi, mixed layer δ30SiDSi values from 2003 and 2013 show significant spatial variability in the magnitude of spring bloom nutrient utilization with lower rates in the north relative to south basin.

A review of the stable isotope bio-geochemistry of the global silicon cycle and its associated trace elements

Silicon (Si) is the second most abundant element in the Earth’s crust and is an important nutrient in the ocean. The global Si cycle plays a critical role in regulating primary productivity and carbon cycling on the continents and in the oceans. Development of the analytical tools used to study the sources, sinks, and fluxes of the global Si cycle (e.g., elemental and stable isotope ratio data for Ge, Si, Zn, etc.) have recently led to major advances in our understanding of the mechanisms and processes that constrain the cycling of Si in the modern environment and in the past. Here, we provide background on the geochemical tools that are available for studying the Si cycle and highlight our current understanding of the marine, freshwater and terrestrial systems. We place emphasis on the geochemistry (e.g., Al/Si, Ge/Si, Zn/Si, δ13 C, δ15 N, δ18 O, δ30 Si) of dissolved and biogenic Si, present case studies, such as the Silicic Acid Leakage Hypothesis, and discuss challenges associated with the development of these environmental proxies for the global Si cycle. We also discuss how each system within the global Si cycle might change over time (i.e., sources, sinks, and processes) and the potential technical and conceptual limitations that need to be considered for future studies.

An experiment to assess the effects of diatom dissolution on oxygen isotope ratios

RATIONALE Current studies which use the oxygen isotope composition from diatom silica (δ(18) Odiatom ) as a palaeoclimate proxy assume that the δ(18) Odiatom value reflects the isotopic composition of the water in which the diatom formed. However, diatoms dissolve post mortem, preferentially losing less silicified structures in the water column and during/after burial into sediments. The impact of dissolution on δ(18) Odiatom values and potential misinterpretation of the palaeoclimate record are evaluated. METHODS Diatom frustules covering a range of ages (6 samples from the Miocene to the Holocene), environments and species were exposed to a weak alkaline solution for 48 days at two temperatures (20 °C and 4 °C), mimicking natural dissolution post mucilage removal. Following treatment, dissolution was assessed using scanning electron microscope images and a qualitative diatom dissolution index. The diatoms were subsequently analysed for their δ(18) O values using step-wise fluorination and isotope ratio mass spectrometry. RESULTS Variable levels of diatom dissolution were observed between the six samples; in all cases higher temperatures resulted in more frustule degradation. Dissolution was most evident in younger samples, probably as a result of the more porous nature of the silica. The degree of diatom dissolution does not directly equate to changes in the isotope ratios; the δ(18) Odiatom value was, however, lower after dissolution, but in only half the samples was this reduction outside the analytical error (2σ analytical error = 0.46‰). CONCLUSIONS We have shown that dissolution can have a small negative impact on δ(18) Odiatom values, causing reductions of up to 0.59‰ beyond analytical error (0.46‰) at natural environmental temperatures. These findings need to be considered in palaeoenvironmental reconstructions using δ(18) Odiatom values, especially when interpreting variations in these values of <1‰.

Holocene carbon dynamics at the forest – steppe ecotone of southern Siberia

Abstract The forest–steppe ecotone in southern Siberia is highly sensitive to climate change; global warming is expected to push the ecotone northwards, at the same time resulting in degradation of the underlying permafrost. To gain a deeper understanding of long‐term forest–steppe carbon dynamics, we use a highly resolved, multiproxy, palaeolimnological approach, based on sediment records from Lake Baikal. We reconstruct proxies that are relevant to understanding carbon dynamics including carbon mass accumulation rates (CMAR; g C m−2 yr−1) and isotope composition of organic matter (δ 13 CTOC). Forest–steppe dynamics were reconstructed using pollen, and diatom records provided measures of primary production from near‐ and off‐shore communities. We used a generalized additive model (GAM) to identify significant change points in temporal series, and by applying generalized linear least‐squares regression modelling to components of the multiproxy data, we address (1) What factors influence carbon dynamics during early Holocene warming and late Holocene cooling? (2) How did carbon dynamics respond to abrupt sub‐Milankovitch scale events? and (3) What is the Holocene carbon storage budget for Lake Baikal. CMAR values range between 2.8 and 12.5 g C m−2 yr−1. Peak burial rates (and greatest variability) occurred during the early Holocene, associated with melting permafrost and retreating glaciers, while lowest burial rates occurred during the neoglacial. Significant shifts in carbon dynamics at 10.3, 4.1 and 2.8 kyr bp provide compelling evidence for the sensitivity of the region to sub‐Milankovitch drivers of climate change. We estimate that 1.03 Pg C was buried in Lake Baikal sediments during the Holocene, almost one‐quarter of which was buried during the early Holocene alone. Combined, our results highlight the importance of understanding the close linkages between carbon cycling and hydrological processes, not just temperatures, in southern Siberian environments.

Biogeochemical cycling in the Bering Sea over the onset of major Northern Hemisphere glaciation

The Bering Sea is one of the most biologically productive regions in the marine system and plays a key role in regulating the flow of waters to the Arctic Ocean and into the subarctic North Pacific Ocean. Cores from IODP Expedition 323 to the Bering Sea provide the first opportunity to obtain reconstructions from the region that extend back to the Pliocene. Previous research at Bowers Ridge, south Bering Sea, has revealed stable levels of siliceous productivity over the onset of major Northern Hemisphere Glaciation (NHG) (c. 2.85-2.73 Ma). However, diatom silica isotope records of oxygen (δ18Odiatom) and silicon (δ30Sidiatom) presented here demonstrate that this interval was associated with a progressive increase in the supply of silicic acid to the region, superimposed on shift to a more dynamic environment characterized by colder temperatures and increased sea ice. This concluded at 2.58 Ma with a sharp increase in diatom productivity, further increases in photic zone nutrient availability and a permanent shift to colder sea surface conditions. These transitions are suggested to reflect a gradually more intense nutrient leakage from the subarctic northwest Pacific Ocean, with increases in productivity further aided by increased sea-ice and wind-driven mixing in the Bering Sea. In suggesting a linkage in biogeochemical cycling between the south Bering Sea and subarctic Northwest Pacific Ocean, mainly via the Kamchatka Strait, this work highlights the need to consider the inter-connectivity of these two systems when future reconstructions are carried out in the region.