[1] Nitrogen isotopes are an important tool for evaluating past biogeochemical cycling from the paleoceanographic record. However, bulk sedimentary nitrogen isotope ratios, which can be determined routinely and at minimal cost, may be altered during burial and early sedimentary diagenesis, particularly outside of continental margin settings. The causes and detailed mechanisms of isotopic alteration are still under investigation. Case studies of the Mediterranean and South China Seas underscore the complexities of investigating isotopic alteration. In an effort to evaluate the evidence for alteration of the sedimentary N isotopic signal and try to quantify the net effect, we have compiled and compared data demonstrating alteration from the published literature. A >100 point comparison of sediment trap and surface sedimentary nitrogen isotope values demonstrates that, at sites located off of the continental margins, an increase in sediment 15 N/ 14 N occurs during early burial, likely at the seafloor. The extent of isotopic alteration appears to be a function of water depth. Depth-related differences in oxygen exposure time at the seafloor are likely the dominant control on the extent of N isotopic alteration. Moreover, the compiled data suggest that the degree of alteration is likely to be uniform through time at most sites so that bulk sedimentary isotope records likely provide a good means for evaluating relative changes in the global N cycle.Citation: Robinson, R. S., et al. (2012), A review of nitrogen isotopic alteration in marine sediments, Paleoceanography, 27, PA4203,

One of the five largest mass extinctions of the past 600 million years occurred at the boundary of the Triassic and Jurassic periods, 201.6 million years ago. The loss of marine biodiversity at the time has been linked to extreme greenhouse warming, triggered by the release of carbon dioxide from flood basalt volcanism in the central Atlantic Ocean. In contrast, the biotic turnover in terrestrial ecosystems is not well understood, and cannot be readily reconciled with the effects of massive volcanism. Here we present pollen, spore and geochemical analyses across the Triassic/Jurassic boundary from three drill cores from Germany and Sweden. We show that gymnosperm forests in northwest Europe were transiently replaced by fern and fern-associated vegetation, a pioneer assemblage commonly found in disturbed ecosystems. The Triassic/Jurassic boundary is also marked by an enrichment of polycyclic aromatic hydrocarbons, which, in the absence of charcoal peaks, we interpret as an indication of incomplete combustion of organic matter by ascending flood basalt lava. We conclude that the terrestrial vegetation shift is so severe and wide ranging that it is unlikely to have been triggered by greenhouse warming alone. Instead, we suggest that the release of pollutants such as sulphur dioxide and toxic compounds such as the polycyclic aromatic hydrocarbons may have contributed to the extinction.

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[1] The Triassic-Jurassic boundary mass-extinction event (T-J; 199.6 Ma) is associated with major perturbations in the carbon cycle recorded in stable carbon isotopes. Two rapid negative isotope excursions in bulk organic carbon (d 13 C org ) occur within the immediate boundary interval at multiple locations and have been linked to the outgassing of 12 C-enriched CO 2 from the Central Atlantic Magmatic Province. In British Columbia, a positive d 13 C org excursion of +5% (Vienna Peedee belemnite (V-PDB)) spans part or all of the subsequent Hettangian stage. Here, we examine the significance of these carbon isotope excursions as records of global carbon cycle dynamics across the T-J boundary and test the link between carbon cycle perturbation-stabilization and biotic extinction-recovery patterns. A combination of d 13 C org and palynological analyses from the Late Triassic to Early Jurassic in the Mingolsheim core (Germany) suggests that organic carbon isotope variations are best explained as the result of both compositional changes in terrestrial versus marine input and disturbance and recovery patterns of major terrestrial plant groups across the T-J boundary. A new high-resolution d 13 C carb record from the Val Adrara section in the Southern Alps (Italy) spanning from the uppermost Rhaetian through Lower Sinemurian does not exhibit a negative excursion at the T-J boundary but does record a large positive d 13 C carb excursion of +4% (V-PDB) in bulk carbonate that begins at the T-J boundary and reaches a local maximum at the Early Late Hettangian boundary. Values then gradually decrease reaching +0.5% at the Hettangian-Sinemurian boundary and remain relatively constant into the Early Sinemurian. Complementary d 13 C carb data from 4 more sections that span the Hettangian-Sinemurian boundary support carbon cycle stabilization within the Upper Hettangian. Our analyses suggest that isotope changes in organic carbon reservoirs do not necessarily require a shift in the global exogenic carbon reservoir and that the positive excursion in the carbonate carbon isotope record is best explained as the combined result of an increase in atmospheric pCO 2 leading to accelerated carbon cycling, decreased skeletal carbonate production, and increased organic carbon burial lasting several hundred thousand years. The termination of the positive inorganic carbon isotope excursion coincides with the recovery of marine skeletal carbonate producers and coeval changes in terrestrial vegetation and reflects the gradual reduction in pCO 2 and the stabilization of the global carbon cycle during the Sinemurian.

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[1] The Triassic-Jurassic (T-J) boundary was one of the largest but least understood mass extinction events in the Phanerozoic. We measured bulk organic nitrogen and carbon isotopes and trace metal concentrations from a core near Mingolsheim (Germany) to infer paleoenvironmental conditions associated with this event. Poorly fossiliferous claystones across the boundary have relatively low d 15 N values and low concentrations of redox-sensitive elements, characteristic of an oxic environment with significant terrestrial input. The Early Jurassic features enrichment in d 15N coincident with high redox-sensitive element concentrations, indicating an increase in water column denitrification and decreased oxygen concentrations. These redox state variations are concordant with shifts in abundance and species composition in terrestrial and marine microflora. We propose that the mass extinction at the T-J boundary was caused by a series of events resulting in a long period of stratification, deep-water hypoxia, and denitrification in this region of the Tethys Ocean basin.

The Cretaceous/Paleogene (K/Pg) mass extinction was associated with a collapse in the carbon isotopic (δ 13 C) gradient between planktonic and benthic foraminifera and a decrease in bulk carbonate δ 13 C values. These perturbations have been explained by several hypotheses: global collapse of primary productivity (Strangelove Ocean), greatly reduced export but not primary productivity (Living Ocean), little or no reduction in export productivity (Resilient Ocean), and geographic heterogeneity in the change of export productivity (Heterogeneous Ocean). We tested primary versus export productivity changes in the paleoshelf of New Jersey, where δ 13 C values and organic carbon accumulation rates can distinguish among different ocean responses. On the shelf, the K/Pg boundary is associated with a~2.5‰ δ 13 C decrease in bulk carbonate, a~0.8‰ δ 13 C decrease in organic carbon, a collapse of the surface to bottom δ 13 C gradient, and a drop in organic carbon accumulation rates. We interpret an early Danian~1.0‰ planktonic foraminiferal δ 13 C gradient, a~0.75‰ cross-shelf benthic foraminiferal δ 13 C gradient, and a drop in carbon accumulation rates to reflect the presence of active primary but limited export productivity, consistent with the Living Ocean hypothesis. We evaluated interbasinal deep-sea benthic foraminiferal δ 13 C gradients between the Pacific (Site 1210) and Atlantic (Site 1262) oceans as a proxy for changes in export productivity. The interbasinal δ 13 C gradient was reduced after the mass extinction, suggesting a reduction in global export productivity. Although our data support the Living Ocean hypothesis, evidence from paleoupwelling zones shows significant export productivity, indicating spatial heterogeneity in the wake of the K/Pg mass extinction (Heterogeneous Ocean).

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