Isotope sample preparation of diatoms for paleoenvironmental research.

Isotopes in diatoms are increasingly used in palaeoenvironmental studies in both lacustrine and marine settings, enabling the reconstruction of a range of variables including temperature, precipitation, salinity, glacial discharge, carbon dynamics and biogeochemical cycling. This protocol details an optimised methodology for extracting diatoms for isotope analysis from sediment samples, using a range of chemical and density separation techniques that minimise sample loss and avoids the need for expensive equipment. Whilst designed for the extraction of diatoms for oxygen, silicon and carbon isotope analysis, additional stages are outlined for the analysis of other isotopes that are of increasing interest to the palaeo community (e.g., boron and zinc). The protocol also includes procedures for assessing sample purity, to ensure that analysed samples produce robust palaeoenvironmental reconstruction. Overall, the method aims to improve the quality of palaeoenvironmental research derived from isotopes in diatoms by maximising sample purity and the efficiency of the extraction process.

Changing nutrient cycling in Lake Baikal, the world's oldest lake.

Lake Baikal, lying in a rift zone in southeastern Siberia, is the world's oldest, deepest, and most voluminous lake that began to form over 30 million years ago. Cited as the "most outstanding example of a freshwater ecosystem" and designated a World Heritage Site in 1996 due to its high level of endemicity, the lake and its ecosystem have become increasingly threatened by both climate change and anthropogenic disturbance. Here, we present a record of nutrient cycling in the lake, derived from the silicon isotope composition of diatoms, which dominate aquatic primary productivity. Using historical records from the region, we assess the extent to which natural and anthropogenic factors have altered biogeochemical cycling in the lake over the last 2,000 y. We show that rates of nutrient supply from deep waters to the photic zone have dramatically increased since the mid-19th century in response to changing wind dynamics, reduced ice cover, and their associated impact on limnological processes in the lake. With stressors linked to untreated sewage and catchment development also now impacting the near-shore region of Lake Baikal, the resilience of the lake's highly endemic ecosystem to ongoing and future disturbance is increasingly uncertain.

Correction: Diatom evidence of 20th century ecosystem change in Lake Baikal, Siberia.

[This corrects the article DOI: 10.1371/journal.pone.0208765.].

Closure of the Bering Strait caused Mid-Pleistocene Transition cooling.

The Mid-Pleistocene Transition (MPT) is characterised by cooling and lengthening glacial cycles from 600-1200 ka, thought to be driven by reductions in glacial CO2 in particular from ~900 ka onwards. Reduced high latitude upwelling, a process that retains CO2 within the deep ocean over glacials, could have aided drawdown but has so far not been constrained in either hemisphere over the MPT. Here, we find that reduced nutrient upwelling in the Bering Sea, and North Pacific Intermediate Water expansion, coincided with the MPT and became more persistent at ~900 ka. We propose reduced upwelling was controlled by expanding sea ice and North Pacific Intermediate Water formation, which may have been enhanced by closure of the Bering Strait. The regional extent of North Pacific Intermediate Water across the subarctic northwest Pacific would have contributed to lower atmospheric CO2 and global cooling during the MPT.

Diatom evidence of 20th century ecosystem change in Lake Baikal, Siberia.

Lake Baikal has been experiencing limnological changes from recent atmospheric warming since the 1950s, with rising lake water temperatures, reduced ice cover duration and reduced lake surface-water mixing due to stronger thermal stratification. This study uses lake sediment cores to reconstruct recent changes (c. past 20 years) in Lake Baikal's pelagic diatom communities relative to previous 20th century diatom assemblage records collected in 1993 and 1994 at the same locations in the lake. Recent changes documented within the core-top diatom records agree with predictions of diatom responses to warming at Lake Baikal. Sediments in the south basin of the lake exhibit clear temporal changes, with the most rapid occurring in the 1990's with shifts towards higher abundances of the cosmopolitan Synedra acus and a decline in endemic species, mainly Cyclotella minuta and Stephanodiscus meyerii and to a lesser extent Aulacoseira baicalensis and Aulacoseira skvortzowii. The north basin, in contrast, shows no evidence of recent diatom response to lake warming despite marked declines in north basin ice cover in recent decades. This study also shows no diatom-inferred evidence of eutrophication from deep water sediments. However, due to the localised impacts seen in areas of Lake Baikal's shoreline from nutrient pollution derived from inadequate sewage treatment, urgent action is vital to prevent anthropogenic pollution extending into the open waters.

Temporal controls on silicic acid utilisation along the West Antarctic Peninsula.

The impact of climatic change along the Antarctica Peninsula has been widely debated in light of atmospheric/oceanic warming and increases in glacial melt over the past half century. Particular concern exists over the impact of these changes on marine ecosystems, not only on primary producers but also on higher trophic levels. Here we present a record detailing of the historical controls on the biogeochemical cycling of silicic acid [Si(OH)4] on the west Antarctica Peninsula margin, a region in which the modern phytoplankton environment is constrained by seasonal sea ice. We demonstrate that Si(OH)4 cycling through the Holocene alternates between being primarily regulated by sea ice or glacial discharge from the surrounding grounded ice sheet. With further climate-driven change and melting forecast for the twenty-first century, our findings document the potential for biogeochemical cycling and multi-trophic interactions along the peninsula to be increasingly regulated by glacial discharge, altering food-web interactions.

Holocene carbon dynamics at the forest-steppe ecotone of southern Siberia.

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 (δ13 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.

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‰.

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 Milankovitch's 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.