Nerilie J. Abram

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme

Carbon dioxide (CO2) is a kinetically and thermodynamically stable molecule. It is easily formed by the oxidation of organic molecules, during combustion or respiration, but is difficult to reduce. The production of reduced carbon compounds from CO2 is an attractive proposition, because carbon-neutral energy sources could be used to generate fuel resources and sequester CO2 from the atmosphere. However, available methods for the electrochemical reduction of CO2 require excessive overpotentials (are energetically wasteful) and produce mixtures of products. Here, we show that a tungsten-containing formate dehydrogenase enzyme (FDH1) adsorbed to an electrode surface catalyzes the efficient electrochemical reduction of CO2 to formate. Electrocatalysis by FDH1 is thermodynamically reversible—only small overpotentials are required, and the point of zero net catalytic current defines the reduction potential. It occurs under thoroughly mild conditions, and formate is the only product. Both as a homogeneous catalyst and on the electrode, FDH1 catalyzes CO2 reduction with a rate more than two orders of magnitude faster than that of any known catalyst for the same reaction. Formate oxidation is more than five times faster than CO2 reduction. Thermodynamically, formate and hydrogen are oxidized at similar potentials, so formate is a viable energy source in its own right as well as an industrially important feedstock and a stable intermediate in the conversion of CO2 to methanol and methane. FDH1 demonstrates the feasibility of interconverting CO2 and formate electrochemically, and it is a template for the development of robust synthetic catalysts suitable for practical applications.

Recent Antarctic Peninsula warming relative to Holocene climate and ice-shelf history

Rapid warming over the past 50 years on the Antarctic Peninsula is associated with the collapse of a number of ice shelves and accelerating glacier mass loss. In contrast, warming has been comparatively modest over West Antarctica and significant changes have not been observed over most of East Antarctica, suggesting that the ice-core palaeoclimate records available from these areas may not be representative of the climate history of the Antarctic Peninsula. Here we show that the Antarctic Peninsula experienced an early-Holocene warm period followed by stable temperatures, from about 9,200 to 2,500 years ago, that were similar to modern-day levels. Our temperature estimates are based on an ice-core record of deuterium variations from James Ross Island, off the northeastern tip of the Antarctic Peninsula. We find that the late-Holocene development of ice shelves near James Ross Island was coincident with pronounced cooling from 2,500 to 600 years ago. This cooling was part of a millennial-scale climate excursion with opposing anomalies on the eastern and western sides of the Antarctic Peninsula. Although warming of the northeastern Antarctic Peninsula began around 600 years ago, the high rate of warming over the past century is unusual (but not unprecedented) in the context of natural climate variability over the past two millennia. The connection shown here between past temperature and ice-shelf stability suggests that warming for several centuries rendered ice shelves on the northeastern Antarctic Peninsula vulnerable to collapse. Continued warming to temperatures that now exceed the stable conditions of most of the Holocene epoch is likely to cause ice-shelf instability to encroach farther southward along the Antarctic Peninsula.

Seasonal Characteristics of the Indian Ocean Dipole during the Holocene epoch

The Indian Ocean Dipole (IOD)—an oscillatory mode of coupled ocean–atmosphere variability—causes climatic extremes and socio-economic hardship throughout the tropical Indian Ocean region. There is much debate about how the IOD interacts with the El Niño/Southern Oscillation (ENSO) and the Asian monsoon, and recent changes in the historic ENSO–monsoon relationship raise the possibility that the properties of the IOD may also be evolving. Improving our understanding of IOD events and their climatic impacts thus requires the development of records defining IOD activity in different climatic settings, including prehistoric times when ENSO and the Asian monsoon behaved differently from the present day. Here we use coral geochemical records from the equatorial eastern Indian Ocean to reconstruct surface-ocean cooling and drought during individual IOD events over the past ∼6,500 years. We find that IOD events during the middle Holocene were characterized by a longer duration of strong surface ocean cooling, together with droughts that peaked later than those expected by El Niño forcing alone. Climate model simulations suggest that this enhanced cooling and drying was the result of strong cross-equatorial winds driven by the strengthened Asian monsoon of the middle Holocene. These IOD–monsoon connections imply that the socioeconomic impacts of projected future changes in Asian monsoon strength may extend throughout Australasia.

Tropical sea surface temperatures for the past four centuries reconstructed from coral archives

Most annually resolved climate reconstructions of the Common Era are based on terrestrial data, making it a challenge to independently assess how recent climate changes have affected the oceans. Here as part of the Past Global Changes Ocean2K project, we present four regionally calibrated and validated reconstructions of sea surface temperatures in the tropics, based on 57 published and publicly archived marine paleoclimate data sets derived exclusively from tropical coral archives. Validation exercises suggest that our reconstructions are interpretable for much of the past 400 years, depending on the availability of paleoclimate data within, and the reconstruction validation statistics for, each target region. Analysis of the trends in the data suggests that the Indian, western Pacific, and western Atlantic Ocean regions were cooling until modern warming began around the 1830s. The early 1800s were an exceptionally cool period in the Indo-Pacific region, likely due to multiple large tropical volcanic eruptions occurring in the early nineteenth century. Decadal-scale variability is a quasi-persistent feature of all basins. Twentieth century warming associated with greenhouse gas emissions is apparent in the Indian, West Pacific, and western Atlantic Oceans, but we find no evidence that either natural or anthropogenic forcings have altered El Nino–Southern Oscillation-related variance in tropical sea surface temperatures. Our marine-based regional paleoclimate reconstructions serve as benchmarks against which terrestrial reconstructions as well as climate model simulations can be compared and as a basis for studying the processes by which the tropical oceans mediate climate variability and change.

Early onset of industrial-era warming across the oceans and continents

The evolution of industrial-era warming across the continents and oceans provides a context for future climate change and is important for determining climate sensitivity and the processes that control regional warming. Here we use post-ad 1500 palaeoclimate records to show that sustained industrial-era warming of the tropical oceans first developed during the mid-nineteenth century and was nearly synchronous with Northern Hemisphere continental warming. The early onset of sustained, significant warming in palaeoclimate records and model simulations suggests that greenhouse forcing of industrial-era warming commenced as early as the mid-nineteenth century and included an enhanced equatorial ocean response mechanism. The development of Southern Hemisphere warming is delayed in reconstructions, but this apparent delay is not reproduced in climate simulations. Our findings imply that instrumental records are too short to comprehensively assess anthropogenic climate change and that, in some regions, about 180 years of industrial-era warming has already caused surface temperatures to emerge above pre-industrial values, even when taking natural variability into account.

Ice core evidence for a 20th century decline of sea ice in the Bellingshausen Sea, Antarctica

[1] This study uses ice core methanesulphonic acid (MSA) records from the Antarctic Peninsula, where temperatures have been warming faster than anywhere else in the Southern Hemisphere, to reconstruct the 20th century history of sea ice change in the adjacent Bellingshausen Sea. Using satellite‐derived sea ice and meteorological data, we show that ice core MSA records from this region are a reliable proxy for regional sea ice change, with years of increased winter sea ice extent recorded by increased ice core MSA concentrations. Our reconstruction suggests that the satellite‐observed sea ice decline in the Bellingshausen Sea during recent decades is part of a long‐term regional trend that has occurred throughout the 20th century. The long‐term perspective on sea ice in the Bellingshausen Sea is consistent with evidence of 20th century warming on the Antarctic Peninsula and may reflect a progressive deepening of the Amundsen Sea Low due to increasing greenhouse gas concentrations and, more recently, stratospheric ozone depletion. As a first‐order estimate, our MSA‐based reconstruction suggests that sea ice in the Bellingshausen Sea has retreated southward by ∼0.7° during the 20th century. Comparison with other 20th century sea ice observations, reconstructions, and model simulations provides a coherent picture of Antarctic sea ice decline during the 20th century, although with regional‐scale differences evident in the timing and magnitude of this sea ice decline. This longer‐term perspective contrasts with the small overall increase in Antarctic sea ice that is observed in post‐1979 satellite data.

Images of diagenetic textures in Porites corals from Papua New Guinea and Indonesia

Diagenesis is now recognized as a potentially major source of error in paleoclimatic reconstructions from fossil and modern coral geochemical records. Key to avoiding spurious results caused by diagenesis is thorough screening of coral material prior to geochemical analysis. In this data brief we present color images from thin sections of fossil and modern Porites corals and demonstrate the effectiveness of thin sections in detecting low levels of diagenesis. The images presented here cover a range of coral preservation levels from pristine aragonite to 100% calcite. We particularly focus on samples containing around 1% diagenetic material, a level known to create artifacts in key climate parameters such as sea surface temperature, and close to the detection limits of other screening methods such as X-ray diffraction (XRD). A qualitative scheme is also presented to rate the degree of diagenesis in a coral, where XRD results are not available or where secondary aragonite is present. Overall, this collection of images is designed as a starting point, in combination with other techniques, to assist in identifying and screening corals for diagenesis.

Intensified decadal variability in tropical climate during the late 19th century

To evaluate and extend the record of decadal climate variability, we present a synthesis of 23 coral oxygen isotope records from the tropical Indo-Pacific that extends back to A. D. 1850. Principal components analysis (PCA) on detrended records reveals a leading pattern of variance with significant interannual (3 - 5 year) and decadal (9 - 14 year) variability. The temporal evolution and spatial pattern of this variability closely resembles the El Nino/Southern Oscillation (ENSO) pattern across both time scales, suggesting that this decadal tropical variability is fundamentally related to ENSO. The 19th century experienced stronger decadal tropical climate variability, compared to the 20th. Decadal variability in the tropical oceans thus remains underestimated by analysis of direct observations. Citation: Ault, T. R., J. E. Cole, M. N. Evans, H. Barnett, N. J. Abram, A. W. Tudhope, and B. K. Linsley (2009), Intensified decadal variability in tropical climate during the late 19th century, Geophys. Res. Lett., 36, L08602, doi: 10.1029/2008GL036924.

A global multiproxy database for temperature reconstructions of the Common Era

Reproducible climate reconstructions of the Common Era (1 CE to present) are key to placing industrial-era warming into the context of natural climatic variability. Here we present a community-sourced database of temperature-sensitive proxy records from the PAGES2k initiative. The database gathers 692 records from 648 locations, including all continental regions and major ocean basins. The records are from trees, ice, sediment, corals, speleothems, documentary evidence, and other archives. They range in length from 50 to 2000 years, with a median of 547 years, while temporal resolution ranges from biweekly to centennial. Nearly half of the proxy time series are significantly correlated with HadCRUT4.2 surface temperature over the period 1850–2014. Global temperature composites show a remarkable degree of coherence between high- and low-resolution archives, with broadly similar patterns across archive types, terrestrial versus marine locations, and screening criteria. The database is suited to investigations of global and regional temperature variability over the Common Era, and is shared in the Linked Paleo Data (LiPD) format, including serializations in Matlab, R and Python.

Variability of sea‐ice in the northern Weddell Sea during the 20th century

The record of winter fast-ice in the South Orkney Islands, northern Weddell Sea, Antarctica is over a century long and provides the longest observational record of sea-ice variability in the Southern Hemisphere. Here we present analyses of the series of fast-ice formation and breakout dates from 1903 to 2008. We show that over the satellite era (post 1979) the timing of both final autumn formation and complete spring breakout of fast-ice is representative of the regional sea-ice concentrations (SIC) in the northern Weddell Sea, and associated with atmospheric conditions in the Amundsen Sea region to the west of the Antarctic Peninsula. Variation in the fast-ice breakout date is influenced by the intensity of the westerly/north-westerly winds associated with the Southern Annular Mode (SAM). In contrast, the date of ice formation displays correlations with regional oceanic and sea-ice conditions over the previous 18 months, which indicate a preconditioning during the previous summer and winter, and exhibits variability associated with variation in tropical Pacific sea-surface temperature (i.e. the El Nino-Sothern Oscillation, ENSO). A reduction in fast-ice duration at the South Orkney Islands around the 1950s was associated with both later formation and earlier breakout. However, there were marked changes in variability (with periodicities of 3-5 year, 7-9 year and 20 year) in each of the series and in their relationships with ENSO and SAM, indicating the need for caution in interpreting changes in ice conditions based on shorter-term satellite series.