Effect of chloride on the chemical conversion of nitrate to nitrous oxide for δ15N analysis

We investigate the influence of chloride concentration on the performance of the chemical reduction method for measurement of the nitrogen isotopic ratio (δ15N) in NO3− in natural waters (McIlvin and Altabet, 2005). In this method, NO3− is first reduced to NO2− using activated cadmium metal, with further reduction to N2O using sodium azide in an acetic acid buffer. N2O is introduced into an isotope ratio mass spectrometer (IRMS) for isotopic measurement. Previously, it was recognized that the presence of halides was necessary for the speed and efficiency of the second step but not thought to be important for the first step. Whereas quantitative Cd reduction of NO3− to NO2− had been noted for seawater samples, here we report, for freshwater and low‐salinity (S 99%) reduction of NO3− to NO2− as well as stable δ15N values that closely matched expected values for standards (within 0.3‰ of standard value). The positive effect of NaCl is likely due to a decrease in free Cd2+ produced over the course of the reaction due to formation of CdCl2

N-loss stoichiometry in a Peru ODZ eddy

Assuming heterotrophic denitrification as the dominant microbial process, Richards (1965) formulated a stoichiometry governing nitrogen loss in open-ocean oxygen deficient zones (ODZs). It prescribes the quantitative coupling between the oxidation of organic matter by NO–3 in the absence of O2 and the corresponding production of CO2, N2, and PO–34. Applied globally, this relationship defines key linkages between the C, N, and P cycles. However, the validity of Richards\u27s stoichiometry is challenged by recognition of complex microbial N processing in ODZs including anammox as an important pathway and nitrite reoxidation. Whereas Richards\u27s stoichiometry would result in N2-N production to NO–3 removal rates of 1.17, dominance by anammox with respect to biogenic N2 production could in theory result in a ratio as high as 2. Ratios with PO–34 production provide an additional constraint on the quantity and composition of respired organic matter. Here we use a mesoscale eddy with extreme N-loss in the Peru ODZ as a natural laboratory to examine N-loss stoichiometry. Its intense biogeochemical signatures, relatively well-defined timescales, and simplified hydrography allowed for the development of strong co-occurring gradients in NO–3, NO–2, biogenic N2, and PO–34. The production of biogenic N2 as compared with the removal of NO–3 (analyzed either directly or as N deficits) was slightly less than predicted by Richards\u27s stoichiometry and did not at all support any excess biogenic N2. PO–34 production, however, was twice the expectation from Richards\u27s stoichiometry suggesting that respired organic matter was P-rich as compared with C:N:P Redfield composition. These results suggest major gaps remain between current understanding of microbial N pathways in ODZs and their net biogeochemical output

Biogeochemical changes within the Benguela Current upwelling system during the Matuyama Diatom Maximum: Nitrogen isotope evidence from Ocean Drilling Program Sites 1082 and 1084

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/95071/1/palo944.pd

Vertical patterns in 15N natural abundance in PON from the surface waters of warm-core rings

The natural abundance of 15N in PON from the upper 200 m of 4 warm-core rings and the Sargasso Sea was measured. Minima in the δ15N of PON often occurred near the depth at which NO3− was first detectable. Frequently, maxima in PON concentration and minima in C/N ratio also co-occurred in this region. The average value for the δ15N of PON below the top of the nitracline was almost always greater than that above the top of the nitracline. The observed vertical pattern for the δ15N of PON is most likely the result of isotopic fractionation in the processes of NO3− uptake by phytoplankton at the base of the euphotic zone and the degradation of PON below the euphotic zone. Variations in the strength and coherence of this vertical pattern appear to occur in response to both rapid physical modification of the water column and the trophic status of the euphotic zone

A model for the vertical flux of nitrogen in the upper ocean: Simulating the alteration of isotopic ratios

An idealized, one-dimensional, constant diffusivity mathematical model for the study of the vertical flux of nitrogen in the upper-ocean is presented. We attempt to simulate observed patterns in vertical profiles for the natural abundance of 15N in particulate organic nitrogen (PON) and the concentrations of PON and NO3−. The concentration of phytoplankton nitrogen (II) increased as a result of either increasing the upward flux of NO3−(N) or by increasing the residence time of II. A minimum in the δ15N of phytoplankton nitrogen (δ2) appeared near a maximum in II at the inflection point of the N profile. Increasing the residence time or the vertical eddy diffusivity, reduced the amplitude of the δ2 profile. The model was able to produce reasonably good simulations of observed profiles from two warm-core rings, Rings 82-E and 82-H, using the most appropriate values for the light extinction coefficient and the residence time of PON. These results lend general support to current views regarding the nature and significance of the vertical fluxes of nitrogen in the upper-ocean and hypotheses presented previously concerning the factors which affect the δ15N of PON

Siderophore and pigment production by Candida albicans

The aim of this project was to study siderophore and pigment production by yeast and hyphal forms of Candida albicans. The ability to form true hyphal cells is virtually unique to C. albicans and the first objective was to identify the best liquid medium capable of yielding pure yeasts or pure hyphae for use in this study. Seven liquid media were tested and overall the results demonstrated that the optimal growth conditions for hyphae are high temperature (3

Simulating the global distribution of nitrogen isotopes in the ocean

We present a new nitrogen isotope model incorporated into the three-dimensional ocean component of a global Earth system climate model designed for millennial timescale simulations. The model includes prognostic tracers for the two stable nitrogen isotopes, 14N and 15N, in the nitrate (NO3−), phytoplankton, zooplankton, and detritus variables of the marine ecosystem model. The isotope effects of algal NO3− uptake, nitrogen fixation, water column denitrification, and zooplankton excretion are considered as well as the removal of NO3− by sedimentary denitrification. A global database of δ15NO3− observations is compiled from previous studies and compared to the model results on a regional basis where sufficient observations exist. The model is able to qualitatively and quantitatively reproduce many of the observed patterns such as high subsurface values in water column denitrification zones and the meridional and vertical gradients in the Southern Ocean. The observed pronounced subsurface minimum in the Atlantic is underestimated by the model presumably owing to too little simulated nitrogen fixation there. Sensitivity experiments reveal that algal NO3− uptake, nitrogen fixation, and water column denitrification have the strongest effects on the simulated distribution of nitrogen isotopes, whereas the effect from zooplankton excretion is weaker. Both water column and sedimentary denitrification also have important indirect effects on the nitrogen isotope distribution by reducing the fixed nitrogen inventory, which creates an ecological niche for nitrogen fixers and, thus, stimulates additional N2 fixation in the model. Important model deficiencies are identified, and strategies for future improvement and possibilities for model application are outlined

Contrasting biogeochemistry of nitrogen in the Atlantic and Pacific oxygen minimum zones

We present new data for the stable isotope ratio ofinorganic nitrogen species from the contrasting oxygen minimum zones (OMZs) of the Eastern Tropical North Atlantic, south of Cape Verde, and the Eastern Tropical South Pacific off Peru. Differences in minimum oxygen concentration and corresponding N-cycle processes for the two OMZs are reflected in strongly contrasting δ15N distributions. Pacific surface waters are marked by strongly positive values for δ15N-NO−3) reflecting fractionation associated withsubsurface N loss and partial NO−3 utilization. This contrasts with negative values in NO−3 depleted surface waters of the Atlantic which are lower than can be explained by N supply via N2 fixation. We suggest the negative values reflect inputs of nitrate, possibly transient, associated withdeposition of Saharan dust. Strong signals of N-loss processes in the subsurfacePacific OMZ are evident in the isotope and N2O data, both ofwhich are compatible with a contribution of canonical denitrification to overall N-loss. However the apparent N isotope fractionation factor observed is relatively low (ɛd=11.4 ‰) suggesting an effect of influence from denitrification in sediments. Identical positive correlation of N2O vs. AOU for waters with oxygen concentrations ([O2]<5 μmol l−1) in both regions reflect a nitrification source. Sharp decrease in N2O concentrations is observed in the Pacific OMZ due to denitrification under oxygen concentrations O2 <5 μmol l−1

Nitrogen cycling in shallow low oxygen coastal waters off Peru from nitrite and nitrate nitrogen and oxygen isotopes

O2 minimum zones (OMZ) of the world's oceans are important locations for microbial dissimilatory NO3- reduction and subsequent loss of combined nitrogen (N) to biogenic N2 gas. This is particularly so when the OMZ is coupled to a region of high productivity leading to high rates of N-loss as found in the coastal upwelling region off Peru. Stable N isotope ratios (and O in the case of NO3- and NO2-) can be used as natural tracers of OMZ N-cycling because of distinct kinetic isotope effects associated with microbially-mediated N-cycle transformations. Here we present NO2- and NO3- stable isotope data from the nearshore upwelling region off Callao, Peru. Subsurface O2 was generally depleted below about 30 m depth with O2 less than 10 μM, while NO2- concentrations were high, ranging from 6 to 10 μM and NO3- was in places strongly depleted to near 0 μM. We observed for the first time, a positive linear relationship between NO2- δ15N and δ18O at our coastal stations, analogous to that of NO3- N and O isotopes during assimilatory and dissimilatory reduction. This relationship is likely the result of rapid NO2- turnover due to higher organic matter flux in these coastal upwelling waters. No such relationship was observed at offshore stations where slower turnover of NO2- facilitates dominance of isotope exchange with water. We also evaluate the overall isotope fractionation effect for N-loss in this system using several approaches that vary in their underlying assumptions. While there are differences in apparent fractionation factor (ε) for N-loss as calculated from the δ15N of [NO3-], DIN, or biogenic N2, values for ε are generally much lower than previously reported, reaching as low as 6.5‰. A possible explanation is the influence of sedimentary N-loss at our inshore stations which incurs highly suppressed isotope fractionation

A review of nitrogen isotopic alteration in marine sediments

Key Points: Use of sedimentary nitrogen isotopes is examined; On average, sediment 15N/14N increases approx. 2 per mil during early burial; Isotopic alteration scales with water depth Abstract: 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 15N/14N 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