N 2 -fixing cyanobacteria play an essential role in sustaining primary productivity in contemporary oceans and freshwater systems. However, the significance of N 2 -fixing cyanobacteria in past nitrogen cycling is difficult to establish as their preservation potential is relatively poor and specific biological markers are presently lacking. Heterocystous N 2 -fixing cyanobacteria synthesize unique long-chain glycolipids in the cell envelope covering the heterocyst cell to protect the oxygen-sensitive nitrogenase enzyme. We found that these heterocyst glycolipids are remarkably well preserved in (ancient) lacustrine and marine sediments, unambiguously indicating the (past) presence of N 2 -fixing heterocystous cyanobacteria. Analysis of Pleistocene sediments of the eastern Mediterranean Sea showed that heterocystous cyanobacteria, likely as epiphytes in symbiosis with planktonic diatoms, were particularly abundant during deposition of sapropels. Eocene Arctic Ocean sediments deposited at a time of large Azolla blooms contained glycolipids typical for heterocystous cyanobacteria presently living in symbiosis with the freshwater fern Azolla, indicating that this symbiosis already existed in that time. Our study thus suggests that heterocystous cyanobacteria played a major role in adding "new" fixed nitrogen to surface waters in past stratified oceans.nitrogen fixation | intact polar lipids | cyanobacterial biomarkers | symbiosis | saproprel

Enormous quantities of the free-floating freshwater fern Azolla grew and reproduced in situ in the Arctic Ocean during the middle Eocene, as was demonstrated by microscopic analysis of microlaminated sediments recovered from the Lomonosov Ridge during Integrated Ocean Drilling Program (IODP) Expedition 302. The timing of the Azolla phase (approximately 48.5 Ma) coincides with the earliest signs of onset of the transition from a greenhouse towards the modern icehouse Earth. The sustained growth of Azolla, currently ranking among the fastest growing plants on Earth, in a major anoxic oceanic basin may have contributed to decreasing atmospheric pCO2 levels via burial of Azolla-derived organic matter. The consequences of these enormous Azolla blooms for regional and global nutrient and carbon cycles are still largely unknown. Cultivation experiments have been set up to investigate the influence of elevated pCO2 on Azolla growth, showing a marked increase in Azolla productivity under elevated (760 and 1910 ppm) pCO2 conditions. The combined results of organic carbon, sulphur, nitrogen content and 15N and 13C measurements of sediments from the Azolla interval illustrate the potential contribution of nitrogen fixation in a euxinic stratified Eocene Arctic. Flux calculations were used to quantitatively reconstruct the potential storage of carbon (0.9-3.5 10(18) gC) in the Arctic during the Azolla interval. It is estimated that storing 0.9 10(18) to 3.5 10(18) g carbon would result in a 55 to 470 ppm drawdown of pCO2 under Eocene conditions, indicating that the Arctic Azolla blooms may have had a significant effect on global atmospheric pCO2 levels through enhanced burial of organic matter.

Editor: P. DeMenocalKeywords: hydrogen isotopes climate modeling hydrological cycling paleoclimate Eocene Azolla Proxy-based climate reconstructions suggest the existence of a strongly reduced equator-to-pole temperature gradient during the Azolla interval in the Early/Middle Eocene, compared to modern. Changes in the hydrological cycle, as a consequence of a reduced temperature gradient, are expected to be reflected in the isotopic composition of precipitation (δD, δ 18 O). The interpretation of water isotopic records to quantitatively reconstruct past precipitation patterns is, however, hampered by a lack of detailed information on changes in their spatial and temporal distribution. Using the isotope-enabled version of the National Center for Atmospheric Research (NCAR) atmospheric general circulation model, Community Atmosphere Model v.3 (isoCAM3), relationships between water isotopes and past climates can be simulated. Here we examine the influence of an imposed reduced meridional sea surface temperature gradient on the spatial distribution of precipitation and its isotopic composition in an Early/Middle Eocene setting. As a result of the applied forcings, the Eocene simulation predicts the occurrence of less depleted high latitude precipitation, with δD values ranging only between 0 and −140‰ (compared to Present-day 0 to −300‰).Comparison with Early/Middle Eocene-age isotopic proxy data shows that the simulation accurately captures the main features of the spatial distribution of the isotopic composition of Early/Middle Eocene precipitation over land in conjunction with the aspects of the modeled Early/Middle Eocene climate. Hence, the included stable isotope module quantitatively supports the existence of a reduced meridional temperature gradient during this interval.

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Chemical products, such as plastics, solvents, and fertilizers, are essential for supporting modern lifestyles. Yet, producing, using, and disposing of chemicals creates adverse environmental impacts which threaten the industry’s license to operate. This study presents seven planet-compatible pathways toward 2050 employing demand-side and supply-side interventions with cumulative total investment costs of US$1.2–3.7 trillion. Resource efficiency and circularity interventions reduce global chemicals demand by 23 to 33% and are critical for mitigating risks associated with using fossil feedstocks and carbon capture and sequestration, and constraints on available biogenic and recyclate feedstocks. Replacing fossil feedstocks with biogenic/air-capture sources, shifting carbon destinations from the atmosphere to ground, and electrifying/decarbonizing energy supply for production technologies could enable net negative emissions of 0.5 GtCO 2eq y −1 across non-ammonia chemicals, while still delivering essential chemical-based services to society.

Chemical products, such as plastics, solvents, and fertilizers, are essential for supporting modern lifestyles. Yet, producing, using and disposing of chemicals creates adverse environmental impacts which threaten the industry's license to operate. This study presents seven planet compatible pathways towards 2050 employing demand-side and supply-side interventions with total investment costs of US$1.2-3.7 billion. Resource efficiency and circularity interventions reduce global chemicals demand by 23–33% and are critical for mitigating risks associated with using fossil feedstocks and carbon capture and sequestration, and constraints on available biogenic and recyclate feedstocks. Replacing fossil feedstocks with biogenic/air-capture sources, shifting carbon destinations from atmosphere to ground, and electrifying/decarbonizing energy supply for production technologies, could enable net negative emissions of 200 MtCO2eq yr-1, while still delivering essential chemical-based services to society.