Estuarine sediments are critical for the remediation of large amounts of anthropogenic nitrogen (N) loading via production of N 2 from nitrate by denitrification. However, nitrate is also recycled within sediments by dissimilatory nitrate reduction to ammonium (DNRA). Understanding the factors that influence the balance between denitrification and DNRA is thus crucial to constraining coastal N budgets. A potentially important factor is the availability of different electron donors (organic carbon, reduced iron and sulfur). Both denitrification and DNRA may be linked to ferrous iron oxidation, however the contribution of Fe(II)-fueled nitrate reduction in natural environments is practically unknown. This study investigated how nitratedependent Fe 21 oxidation affects the partitioning between nitrate reduction pathways using 15 N-tracing methods in sediments along the salinity gradient of the periodically hypoxic Yarra River estuary, Australia. Increased dissolved Fe 21 availability resulted in significant enhancement of DNRA rates from around 10-20% total nitrate reduction in control incubations to over 40% in those with additional Fe 21 , at several sites.Increases in DNRA at some locations were accompanied by reductions in denitrification. Significant correlations were observed between Fe 21 oxidation and DNRA rates, with reaction ratios corresponding to the stoichiometry of Fe 21

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Growth of large phytoplankton is considered to be diffusion limited at low nutrient concentrations, yet their constraints and contributions to carbon (C) and nitrogen fluxes in field plankton communities are poorly quantified under this condition. Using secondary ion mass spectrometry (SIMS), we quantified cell-specific assimilation rates of C, nitrate, and ammonium in summer communities of large phytoplankton when dissolved inorganic nitrogen concentrations are low in temperate coastal regions. Chain-forming diatoms composed 6% of total particulate organic carbon, but contributed 20% of C assimilation, 54% of nitrate assimilation and 32% of ammonium assimilation within the plankton community. In contrast, large dinoflagellates composed 11% of total POC, and contributed 14% of the C assimilation, 4% of ammonium and 9% of nitrate assimilation within the plankton community. Measured cell-specific C and nitrate assimilation rate match the Redfield ratio and the maximal nitrate assimilation in Chaetoceros spp. predicted by mass transfer theory. However, average ammonium assimilation rates were 30 and 340% higher than predicted by mass transfer theory in Tripos/Ceratium and Chaetoceros, respectively, suggesting that microbial interactions in the phycosphere may facilitate substantial luxury ammonium uptake by Chaetoceros in environments with fluctuating nitrate concentrations.

Determining accurate rates of benthic nitrogen (N) removal and retention pathways from diverse environments is critical to our understanding of process distribution and constructing reliable N budgets and models. The whole‐core 15N isotope pairing technique (IPT) is one of the most widely used methods to determine rates of benthic nitrate‐reducing processes and has provided valuable information on processes and factors controlling N removal and retention in aquatic systems. While the whole core IPT has been employed in a range of environments, a number of methodological and environmental factors may lead to the generation of inaccurate data and are important to acknowledge for those applying the method. In this review, we summarize the current state of the whole core IPT and highlight some of the important steps and considerations when employing the technique. We discuss environmental parameters which can pose issues to the application of the IPT and may lead to experimental artifacts, several of which are of particular importance in environments heavily impacted by eutrophication. Finally, we highlight the advances in the use of the whole‐core IPT in combination with other methods, discuss new potential areas of consideration and encourage careful and considered use of the whole‐core IPT. With the recognition of potential issues and proper use, the whole‐core IPT will undoubtedly continue to develop, improve our understanding of benthic N cycling and allow more reliable budgets and predictions to be made.