[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,

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Abstract. The enhanced accumulation of organic matter in Eastern Mediterranean sapropels and their unusually low δ 15 N values have been attributed to either enhanced nutrient availability which led to elevated primary production and carbon sequestration or to enhanced organic matter preservation under anoxic conditions. In order to evaluate these two hypothesis we have determined Ba/Al ratios, amino acid composition, N and organic C concentrations and δ 15 N in sinking particles, surface sediments, eight spatially distributed core records of the youngest sapropel S1 (10-6 ka) and older sapropels (S5, S6) from two locations. These data suggest that (i) temporal and spatial variations in δ 15 N of sedimentary N are driven by different degrees of diagenesis at different sites rather than by changes in N-sources or primary productivity and (ii) present day TOC export production would suffice to create a sapropel like S1 under conditions of deepwater anoxia. This implies that both enhanced TOC accumulation and 15 N depletion in sapropels were due to the absence of oxygen in deep waters. Thus preservation plays a major role for the accumulation of organic-rich sediments casting doubt on the need of enhanced primary production for sapropel formation.

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The fine-scale depth distribution of major carbon pools and their stable carbon isotopic signatures (delta(13)C) were determined in a cyanobacterial mat (Salin-de-Giraud, Camargue, France) to study early diagenetic alterations and the carbon preservation potential in hypersaline mat ecosystems. Particular emphasis was placed on the geochemical role of extracellular polymeric substances (EPS). Total carbon (C(tot)), organic carbon (C(org)), total nitrogen (N(tot)), total hydrolysable amino acids (THAA), carbohydrates, cyanobacteria-derived hydrocarbons (8-methylhexadecane, n-heptadec-5-ene, n-heptadecane) and EPS showed highest concentrations in the top millimetre of the mat and decreased with depth. The hydrocarbons attributed to cyanobacteria showed the strongest decrease in concentration with depth. This correlated well with the depth profiles of oxygenic photosynthesis and oxygen, which were detected in the top 0.6 and 1.05 mm, respectively, at a high down-welling irradiance (1441 micromol photons m(-2) s(-1)). At depths beneath the surface layer, the C(org) was composed mainly of amino acids and carbohydrates. A resistance towards microbial degradation could have resulted from interactions with diverse functional groups present in biopolymers (EPS) and with minerals deposited in the mat. A (13)C enrichment with depth for the total carbon pool (C(tot)) was observed, with delta(13)C values ranging from -16.3 per thousand at the surface to -11.3 per thousand at 9-10 mm depth. Total lipids depicted a delta(13)C value of -17.2 per thousand in the top millimetre and then became depleted in (13)C with depth (-21.7 to -23.3 per thousand). The delta(13)C value of EPS varied only slightly with depth (-16.1 to -17.3 per thousand) and closely followed the delta(13)C value of C(org) at depths beneath 4 mm. The EPS represents an organic carbon pool of preservation potential during early stages of diagenesis in recent cyanobacterial mats as a result of a variety of possible interactions. Their analyses might improve our understanding of fossilized microbial remains from mat ecosystems.