The ability of scleractinian corals to thrive in the oligotrophic (low-nutrient, low-productivity) surface waters of the tropical ocean is commonly attributed to their symbiotic relationship with photosynthetic dinoflagellates 1,2 . The evolutionary history of this symbiosis might clarify its organismal and environmental roles. It is currently unclear whether photosymbiosis first arose in the Triassic, with the emergence of scleractinian corals, or if it was already prevalent amongst older coral groups that have since gone extinct 3–5 . Here, we report the first measurements of nitrogen isotope ratios of coral-bound organic matter (CB-δ 15 N) in samples from Mid-Devonian reefs (Givetian, ca. 385 Ma), which represent the oldest isotopic constraint on the evolution of photosymbiosis to date. The colonial tabulate and loosely colonial (dendroid) corals analyzed have low CB-δ 15 N values (1.59‰±0.53‰ and 1.45±0.66‰, respectively) in comparison with co-occurring solitary rugose corals (4.38‰±1.34‰). The isotopic difference between Devonian colonial and solitary corals (2.86‰±0.86‰) is statistically indistinguishable from that observed between modern symbiont-bearing and symbiont-barren corals (3.38‰±1.05‰). From this evidence we infer that Mid-Devonian colonial tabulate and loosely colonial (dendroid) corals hosted active photosymbionts, while solitary rugose corals did not. The low CB-δ 15 N values of the Devonian colonial tabulate and dendroid corals relative to the modern range suggest that Devonian reefs formed in biogeochemical regimes analogous to the modern oligotrophic subtropical gyres. Widespread oligotrophy during the Devonian likely may have promoted coral photosymbiosis, potentially explaining why Devonian reefs were the most productive reef ecosystems of the Phanerozoic.

The analysis of the nitrogen (N) isotopic composition of organic matter bound to fossil biomineral structures (BB-δ15 N) using the oxidation-denitrifier (O-D) method provides a novel tool to study past changes in N cycling processes.METHODS:We report a set of methodological improvements to the O-D method, including (a) a method for sealing the reaction vials in which the oxidation of organic N to NO3 - takes place, (b) a recipe for bypassing the pH adjustment step before the bacterial conversion of NO3 - to N2 O, and (c) a method for storing recrystallized dipotassium peroxodisulfate (K2 S2 O8 ) under Ar atmosphere.RESULTS:The new sealing method eliminates the occasional contamination and vial breakage that occurred previously while increasing sample throughput. The protocol for bypassing pH adjustment does not affect BB-δ15 N, and it significantly reduces the processing time. Storage of K2 S2 O8 reagent under Ar atmosphere produces stable oxidation blanks over more than 3.5 years. We report analytical blanks, accuracy, and precision for this methodology from eight users over the course of ~3.5 years of analyses at the Max Planck Institute for Chemistry. Our method produces analytical blanks characterized by low N content (0.30 ± 0.13 nmol N, 1σ, n = 195) and stable δ15 N (-2.20 ± 3.13‰, n = 195). The analysis of reference amino acid standards USGS 40 and USGS 65 indicates an overall accuracy of -0.23 ± 0.35‰ (1σ, n = 891). The analysis of in-house fossil standards gives similar analytical precision (1σ) across a range of BB-δ15 N values and biominerals: zooxanthellate coral standard PO-1 (6.08 ± 0.21‰, n = 267), azooxanthellate coral standard LO-1 (10.20 ± 0.28‰, n = 258), foraminifera standard MF-1 (5.92 ± 0.28‰, n = 243), and tooth enamel AG-Lox (4.06 ± 0.49‰, n = 78).CONCLUSIONS:The methodological improvements significantly increase sample throughput without compromising analytical precision or accuracy down to 1 nmol of N.

The proposed Anthropocene Global Boundary Stratotype Section and Point (GSSP) candidate site of West Flower Garden Bank (27.8762°N, 93.8147°W) is an open ocean location in the Gulf of Mexico with a submerged coral reef and few direct human impacts. Corals contain highly accurate and precise (<±1 year) internal chronologies, similar to tree rings, and their exoskeletons are formed of aragonite and can be preserved in the rock record. Here we present results from a large Siderastrea siderea coral (core 05WFGB3; 1755–2005 CE) sampled with annual and monthly resolutions that show clear markers of global and regional human impacts. Atmospheric nuclear bomb testing by-products (14C, 239+240Pu) have clear increases in this coral starting in 1957 for 14C and the first increase in 1956 for 239+240Pu (potential bases for the Anthropocene GSSP). Coral δ13C declined especially after 1956 consistent with the Suess effect resulting from the burning of fossil fuels. Coral skeletal δ15N starts to increase in 1963 corresponding with the increase in agricultural fertilizers. Coral Hg concentrations (1933–1980) loosely track fluctuations in industrial pollution and coral Ba/Ca increases from 1965–1983 when offshore oil operations expand after 1947. Coral temperature proxies contain the 20th-century global warming trend whereas coral growth declines during this interval.

Fossil‐bound organic material holds great potential for the reconstruction of past changes in nitrogen (N) cycling. Here, with a series of laboratory experiments, we assess the potential effect of oxidative degradation, fossil dissolution, and thermal alteration on the fossil‐bound N isotopic composition of different fossil types, including deep and shallow water scleractinian corals, foraminifera, diatoms and tooth enamel. Our experiments show that exposure to different oxidizing reagents does not significantly affect the N isotopic composition or N content of any of the fossil types analyzed, demonstrating that organic matter is well protected from changes in the surrounding environment by the mineral matrix. In addition, we show that partial dissolution (of up to 70%–90%) of fossil aragonite, calcite, opal, or enamel matrixes has a negligible effect on the N isotopic composition and N content of the fossils. These results suggest that the isotopic composition of fossil‐bound organic material is relatively uniform, and also that N exposed during dissolution is lost without significant isotopic discrimination. Finally, our heating experiments show negligible changes in the N isotopic composition and N content of all fossil types at 100°C. At 200°C and hotter, any N loss and associated nitrogen isotope changes appear to be directly linked to the sensitivity of the mineral matrix to thermal stress, which depends on the biomineral type. These results suggest that, so long as high temperature does not compromise the mineral structure, the biomineral matrix acts as a closed system with respect to N, and the N isotopic composition of the fossil remains unchanged.