It is quite challenging to realize fluorescence resonance energy transfer (FRET) between two chromophores with specific positions and directions. Herein, through the self-assembly of two carefully selected fluorescent ligands via metal-coordination interactions, we prepared two tetragonal prismatic platinum(II) cages with a reverse FRET process between their faces and pillars. Bearing different responses to external stimuli, these two emissive ligands are able to tune the FRET process, thus making the cages sensitive to solvents, pressure, and temperature. First, these cages could distinguish structurally similar alcohols such as n-butanol, t-butanol, and ibutanol. Furthermore, they showed decreased emission with bathochromic shifts under high pressure. Finally, they exhibited a remarkable ratiometric response to temperature over a wide range (223-353 K) with high sensitivity. For example, by plotting the ratio of the maximum emission (I 600 /I 480 ) of metallacage 4b against the temperature, the slope reaches 0.072, which is among the highest values for ratiometric fluorescent thermometers reported so far. This work not only offers a strategy to manipulate the FRET efficiency in emissive supramolecular coordination complexes but also paves the way for the future design and preparation of smart emissive materials with external stimuli responsiveness.

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The Southern Ocean regulates the ocean’s biological sequestration of CO2 and is widely suspected to underpin much of the ice age decline in atmospheric CO2 concentration, but the specific changes in the region are debated. Although more complete drawdown of surface nutrients by phytoplankton during the ice ages is supported by some sediment core-based measurements, the use of different proxies in different regions has precluded a unified view of Southern Ocean biogeochemical change. Here, we report measurements of the 15N/14N of fossil-bound organic matter in the stony deep-sea coral Desmophyllum dianthus, a tool for reconstructing surface ocean nutrient conditions. The central robust observation is of higher 15N/14N across the Southern Ocean during the Last Glacial Maximum (LGM), 18–25 thousand years ago. These data suggest a reduced summer surface nitrate concentration in both the Antarctic and Subantarctic Zones during the LGM, with little surface nitrate transport between them. After the ice age, the increase in Antarctic surface nitrate occurred through the deglaciation and continued in the Holocene. The rise in Subantarctic surface nitrate appears to have had both early deglacial and late deglacial/Holocene components, preliminarily attributed to the end of Subantarctic iron fertilization and increasing nitrate input from the surface Antarctic Zone, respectively

With the rapid rise in pollution-associated nitrogen inputs to the western Pacific, it has been suggested that even the open ocean has been affected. In a coral core from Dongsha Atoll, a remote coral reef ecosystem, we observe a decline in the N/N of coral skeleton-bound organic matter, which signals increased deposition of anthropogenic atmospheric N on the open ocean and its incorporation into plankton and, in turn, the atoll corals. The first clear change occurred just before 2000 CE, decades later than predicted by other work. The amplitude of change suggests that, by 2010, anthropogenic atmospheric N deposition represented 20 ± 5% of the annual N input to the surface ocean in this region, which appears to be at the lower end of other estimates.

The million-year variability of the marine nitrogen cycle is poorly understood. Before 57 million years (Ma) ago, the 15N/14N ratio (δ15N) of foraminifera shell-bound organic matter from three sediment cores was high, indicating expanded water column suboxia and denitrification. Between 57 and 50 Ma ago, δ15N declined by 13 to 16 per mil in the North Pacific and by 3 to 8 per mil in the Atlantic. The decline preceded global cooling and appears to have coincided with the early stages of the Asia-India collision. Warm, salty intermediate-depth water forming along the Tethys Sea margins may have caused the expanded suboxia, ending with the collision. From 50 to 35 Ma ago, δ15N was lower than modern values, suggesting widespread sedimentary denitrification on broad continental shelves. δ15N rose at 35 Ma ago, as ice sheets grew, sea level fell, and continental shelves narrowed.

Worldwide dam building in large river basins has substantially altered the carbon cycle by trapping much of the riverine transported particulate organic carbon (POC) in terrestrial reservoirs. Here we take the Changjiang (Yangtze) River basin, in which~50,000 dams were built over the past 50 years, as an example to evaluate the effect of dam building on POC sequestration. We report the characteristics (elemental composition, radiocarbon and stable carbon isotopic compositions, and Raman spectra) of bulk POC in the lower Changjiang from October 2007 to September 2008, and we estimate the POC sequestration induced by dam building since the 1950s for the Changjiang Basin. Using radiocarbon measurements, we quantify the fraction of biospheric POC (POC bio ) and petrogenic POC (POC petro ) in Changjiang POC. Over the study period, around 25% of the Changjiang POC is radiocarbon-dead POC petro ; the remaining is POC bio with a mean radiocarbon age of~3.5 kyr. Studies on the East China Sea (ECS) shelf along with an oxidation experiment suggest that, prior to dam building, the Changjiang POC bio was significantly oxidized in the ECS margin. In contrast, high preservation of POC is observed in Changjiang reservoirs. Combining our POC data with hydrometric data sets, our study indicates that, over the past five decades, dam building may have largely shifted the Changjiang POC burial site from the ECS margin to terrestrial reservoirs. This shift in burial site preserved labile POC bio that would have been oxidized, suggesting a new temporary carbon sink. We estimate that dam building in the Changjiang has sequestered~4.9 ± 1.9 megatons POC bio every year since 2003, approximately 10% of the global riverine POC burial flux to the oceans.

New isotopic and microstructural data suggest that the Tethyan Triassic corals were predominantly photosymbiotic.

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