Comparison of nitrogen isotopic values from different preparation methods

We are writing to comment on the work of Tamburini et al. (2003, doi:10.1029/2000PA000616). During the course of subsequent discussions between the authors and ourselves, it has become clear that the published sedimentary nitrogen isotopic values for Ocean Drilling Program (ODP) Site 724 are in error. Our reanalysis of sediment samples from the same intervals has revealed a significant offset from the original d15N data, requiring a revised assessment of their initial interpretation. The purposes of this comment are to (1) address the origin of these errors; (2) outline a protocol for future validation of nitrogen isotopic analyses; and (3) provide revised interpretations of the sedimentary d15N data in terms of the regional relative contributions of denitrification and nitrogen fixation and mean state of the southwest monsoon. (2) Nitrogen isotopic values measured on late Quaternary sediments at Arabian Sea ODP Site 724 by Tamburini et al. (2003, doi:10.1029/2000PA000616) are inexplicably different from a number of published records of d15N from very nearby on the Oman margin (Altabet et al., 1995, doi:10.1038/373506a0; 1999, doi:10.1029/1999PA900035; 2002, doi:10.1038/415159a; Higginson et al., 2004, doi:10.1016/j.gca.2004.03.015) and elsewhere in the Arabian Sea (Reichart et al., 1998, doi:10.1029/98PA02203). These data were generated using similar instrumentation (elemental analyzer coupled with an isotope ratio mass spectrometer) and analytical methodology to those already published. Concerned by this clear discrepancy, we analyzed aliquots of sediment from the same depth intervals for nitrogen abundance and bulk sedimentary nitrogen isotopes. We have been unable to duplicate the values published by Tamburini et al. (2003, doi:10.1029/2000PA000616 ), even after analysis of multiple replicates and due consideration of natural sediment heterogeneities and postrecovery sample storage.

Table 1: Densities of nitrate-dissimilating and nitrite-dissimilating bacteria in surface sediments in the German Bight, North Sea

At 24 stations in the Weser Estuary and the German Bight the Most Probable Numbers (MPN/g dry wt. sediment) of nitrate-dissimilating (= denitrifying) and of nitrate plus nitrite-dissimilating bacteria were recorded. The numbers of nitrite-dissimilating bacteria, i. e. denitrifiers not capable of reducing nitrate to nitrite, were calculated by subtraction of the MPN for nitrate-dissimilating from the MPN of nitrate plus nitrite-dissimilating bacteria. By determining the percentages of these bacteria in relation to the number of the heterotrophs, the ecological importance of denitrification, especially the nitrite dissimilation, was estimated. The results showed the MPN of nitrate-dissimilating bacteria to be in the range of 0-156 (up to 0.8 % of heterotrophic bacteria). An exception was the sediment of one station with a MPN of 1849, or 5.2 % of the heterotrophs. The amounts of nitrite-dissimilating bacteria were between 0 and 2352 (up to 13 % of heterotrophic bacteria). In the estuary the numbers of nitrate-dissimilating and of nitrite-dissimilating bacteria showed a decreasing tendency with distance from Bremerhaven. The highest numbers were found in the Weser off Bremerhaven and also at 3 stations in the German Bight, south of the Isle of Helgoland.

(Table 1) N-isotope record of planktonc foraminifera of sediment core MD02-2550C2

Constraining variations in marine N2-fixation over glacial-interglacial timescales is crucial for determining the role of the marine nitrogen cycle in modifying ocean productivity and climate, yet paleo-records from N2-fixation regions are sparse. Here we present new nitrogen isotope (d15N) records of bulk sediment and foraminifera test-bound (FB) nitrogen extending back to the last ice age from the oligotrophic Gulf of Mexico (GOM). Previous studies indicate a substantial terrestrial input during the last ice age and early deglacial, for which we attempt to correct the bulk sediment d15N using its observed relationship with the C/N ratio. Both corrected bulk and FB-d15N reveal a substantial glacial-to-Holocene decrease of d15N toward Holocene values of around 2.5 per mil, similar to observations from the Caribbean. This d15N change is most likely due to a glacial-to-Holocene increase in regional N2-fixation. A deglacial peak in the FB-d15N of thermocline dwelling foraminifera Orbulina universa probably reflects a whole ocean increase in the d15N of nitrate during deglaciation. The d15N of the surface dwelling foraminifera Globigerinoides ruber and the corrected bulk d15N show little sign of this deglacial peak, both decreasing from last glacial values much earlier than does the d15N of O. universa; this may indicate that G. ruber and bulk N reflect the euphotic zone signal of an early local increase in N2-fixation. Our results add to the evidence that, during the last ice age, the larger iron input from dust did not lead to enhanced N2-fixation in this region. Rather, the glacial-to-Holocene decrease in d15N is best explained by a response of N2-fixation within the Atlantic to the deglacial increase in global ocean denitrification.

Bulk 15N, and 13Corg ratios, and calculation of unutilized nitrate of surface samples off the southwest coast of Africa (Table 1)

Bulk delta15N values in surface sediment samples off the southwestern coast of Africa were measured to investigate the biogeochemical processes occurring in the water column. Nitrate concentrations and the degree of utilization of the nitrate pool are the predominant controls on sedimentary delta15N in the Benguela Current region. Denitrification does not appear to have had an important effect on the delta15N signal of these sediments and, based on delta15N and delta13C, there is little terrestrial input.

Distribution of surface sediment properties along the Portuguese western margin

Organic matter contained in surface sediments from four regions on the western Portuguese shelf, which are influenced by coastal upwelling and fluvial input, was analysed with respect to elemental organic carbon (Corg) and nitrogen (Ntotal) content and isotopic carbon and nitrogen ratios (d13Corg, d15N). Corg/Ntotal weight ratios and d13Corg values are interpreted in terms of terrigenous or marine organic matter sources, supported by CaCO3 content. Organic matter in the shelf sediments is mainly of marine origin, with increasing terrigenous components only close to rivers and estuaries. In the northern shelf region the data indicates significant terrigenous supply by the Douro River. North of the Nazaré Canyon organic matter composition implies a mainly marine origin, with a higher terrestrial influence close to the canyon head. Organic matter composition in the central shelf region, which is dominated by the Tagus Estuary and the Tagus prodelta, reveals a change from a continental-type signature within the estuary to a more marine-type signature further to the west and south of the estuary mouth. In the southern region near Cape Sines the geochemical properties clearly reflect the marine origin of sedimentary organic matter. Sedimentary d15N values are interpreted to reflect various degrees of assimilation of seasonally upwelled nitrate, in relation to the upwelling centres. In the estuarine environment, inputs of agriculturally influenced dissolved inorganic nitrogen are reflected in the sediments. No evidence for N2-fixation or denitrification is found. On the central shelf north of the Nazaré canyon, sedimentary d15N values are close to marine d15NO3- and thus indicate a complete NO3- assimilation and N-limitation of marine production. Light d15N values in distal sediments off the Douro River mouth and in samples south of C. Sines reflect high NO3- supply and a close proximity to the seasonal upwelling centres. Particularly in sediments form the Sines region, light d15N values in southern samples reflect stronger upwelling further south.

(Table 1) Bulk Fe isotope values and pyrite framboids sizes of Cenomanian-Turonian samples

Organic carbon-rich shales from localities in England, Italy, and Morocco, which formed during the Cenomanian-Turonian oceanic anoxic event (OAE), have been examined for their total organic carbon (TOC) values together with their carbon, nitrogen, and iron isotope ratios. Carbon isotope stratigraphy (d13Corg and d13Ccarb) allows accurate recognition of the strata that record the oceanic anoxic event, in some cases allowing characterization of isotopic species before, during, and after the OAE. Within the black shales formed during the OAE, relatively heavy nitrogen isotope ratios, which correlate positively with TOC, suggest nitrate reduction (leading ultimately to denitrification and/or anaerobic ammonium oxidation). Black shales deposited before the onset of the OAE in Italy have unusually low bulk d57Fe values, unlike those found in the black shale (Livello Bonarelli) deposited during the oceanic anoxic event itself: These latter conform to the Phanerozoic norm for organic-rich sediments. Pyrite formation in the pre-OAE black shales has apparently taken place via dissimilatory iron reduction (DIR), within the sediment, a suboxic process that causes an approximately -2 per mil fractionation between a lithogenic Fe(III)oxide source and Fe(II)aq. In contrast, bacterial sulfate reduction (BSR), at least partly in the water column, characterized the OAE itself and was accompanied by only minor iron isotope fractionation. This change in the manner of pyrite formation is reflected in a decrease in the average pyrite framboid diameter from ~10 to ~7 µm. The gradual, albeit irregular increase in Fe isotope values during the OAE, as recorded in the Italian section, is taken to demonstrate limited isotopic evolution of the dissolved iron pool, consequent upon ongoing water column precipitation of pyrite under euxinic conditions. Given that evidence exists for both nitrate and sulfate reduction during the OAE, it is evident that redox conditions in the water column were highly variable, in both time and space.

Wastewater treatment by novel hybrid biological – ion exchange processes

This study presents two novel methods for treating important environmental contaminants from two different wastewater streams. One process utilizes the kinetic advantages and reliability of ion exchanging clinoptilolite in combination with biological treatment to remove ammonium from municipal sewage. A second process, HAMBgR (Hybrid Adsorption Membrane Biological Reactor), combines both ion exchange resin and bacteria into a single reactor to treat perchlorate contaminated waters. Combining physicochemical adsorptive treatment with biological treatment can provide synergistic benefits to the overall removal processes. Ion exchange removal solves some of the common operational reliability limitations of biological treatment, like slow response to environmental changes and leaching. Biological activity can in turn help reduce the economic and environmental challenges of ion exchange processes, like regenerant cost and brine disposal. The second section of this study presents continuous flow column experiments, used to demonstrate the ability of clinoptilolite to remove wastewater ammonium, as well as the effectiveness of salt regeneration using highly concentrated sea salt solutions. The working capacity of clinoptilolite more than doubled over the first few loading cycles, while regeneration recovered more than 98% of ammonium. Using the regenerant brine for subsequent halotolerant algae growth allowed for its repeated use, which could lead to cost savings and production of valuable algal biomass. The algae were able to uptake all ammonium in solution, and the brine was able to be used again with no loss in regeneration efficiency. This process has significant advantages over conventional biological nitrification; shorter retention times, wider range of operational conditions, and higher quality effluent free of nitrate. Also, since the clinoptilolite is continually regenerated and the regenerant is rejuvenated by algae, overall input costs are expected to be low. The third section of this study introduces the HAMBgR process for the elimination of perchlorate and presents batch isotherm experiments and pilot reactor tests. Results showed that a variety of ion-exchange resins can be effectively and repeatedly regenerated biologically, and maintain an acceptable working capacity. The presence of an adsorbent in the HAMBgR process improved bioreactor performance during operational fluctuations by providing a physicochemical backup to the biological process. Pilot reactor tests showed that the HAMBgR process reduced effluent perchlorate spikes by up to 97% in comparison to a conventional membrane bio-reactor (MBR) that was subject to sudden changes in influent conditions. Also, the HAMBgR process stimulated biological activity and lead to higher biomass concentrations during increased contaminant loading conditions. Conventional MBR systems can be converted into HAMBgR’s at a low cost, easily justifiable by the realized benefits. The concepts employed in the HAMBgR process can be adapted to treat other target contaminants, not just perchlorate.

Nitrogen use efficiency in summer sorghum grown on clay soils

Nitrogen fertilizer inputs dominate the fertilizer budget of grain sorghum growers in northern Australia, so optimizing use efficiency and minimizing losses are a primary agronomic objective. We report results from three experiments in southern Queensland sown on contrasting soil types and with contrasting rotation histories in the 2012-2013 summer season. Experiments were designed to quantify the response of grain sorghum to rates of N fertilizer applied as urea. Labelled 15N fertilizer was applied in microplots to determine the fate of applied N, while nitrous oxide (N2O) emissions were continuously monitored at Kingaroy (grass or legume ley histories) and Kingsthorpe (continuous grain cropping). Nitrous oxide is a useful indicator of gaseous N losses. Crops at all sites responded strongly to fertilizer N applications, with yields of unfertilized treatments ranging from 17% to 52% of N-unlimited potential. Maximum yields ranged from 4500 (Kupunn) to 5450 (Kingaroy) and 8010 (Kingsthorpe) kg/ha. Agronomic efficiency (kg additional grain produced/kg fertilizer N applied) at the optimum N rate on the Vertosol sites was 23 (80 N, Kupunn) to 25 (160N, Kingsthorpe), but 40-42 on the Ferrosols at Kingaroy (70-100N). Cumulative N2O emissions ranged from 0.44% (Kingaroy legume) to 0.93% (Kingsthorpe) and 1.15% (Kingaroy grass) of the optimum fertilizer N rate at each site, with greatest emissions from the Vertosol at Kingsthorpe. The similarity in N2O emissions factors between Kingaroy and Kingsthorpe contrasted markedly with the recovery of applied fertilizer N in plant and soil. Apparent losses of fertilizer N ranged from 0-5% (Ferrosols at Kingaroy) to 40-48% (Vertosols at Kupunn and Kingsthorpe). The greater losses on the Vertosols were attributed to denitrification losses and illustrate the greater risks of N losses in these soils in wet seasonal conditions.

Avaliação da fertilização azotada na produtividade e qualidade da variedade Hermes para indústria

O azoto é determinante na produtividade e na qualidade da batata para indústria. Com este trabalho pretendeu-se avaliar o efeito de diferentes doses de azoto na variedade de batata “Hermes”, em plena condições de cultivo do Vale do Tejo. Os tratamentos consistiram na aplicação de 0 (N0), 80 (N80), 160 (N160), 240 (N240) e 320 (N320) kg de azoto/ha, na forma de ENTECÒ 26. O ensaio foi instalado em parcelas totalmente aleatórias, com 4 repetições. Foi registado semanal a taxa de cobertura de solo pelo método da grelha até à sua cobertura total. Bissemanalmente, foram recolhidas plantas nos tratamentos N0 (0kgN/ha) e N160 (160kgN/ha) para avaliação do seu desenvolvimento e crescimento. No final do ciclo cultural avaliou-se a produção total, comercial, em peso e número de tubérculos. Avaliou-se ainda o peso específico, os teores em matéria seca dos tubérculos e a percentagem do azoto total na matéria seca das folhas e tubérculos. A adubação azotada influenciou a dimensão do aparelho fotossintético, através do estímulo de ramificações. Verificou-se uma maior produtividade de tubérculos nos tratamentos com maior aplicação de azoto, embora os acréscimos tenham sido menores a partir dos 160kg/ha. O azoto influenciou a percentagem de tubérculos de maior calibre.

Microbial nitrogen dynamics in organic and mineral soil horizons along a latitudinal transect in western Siberia

Soil N availability is constrained by the breakdown of N-containing polymers such as proteins to oligopeptides and amino acids that can be taken up by plants and microorganisms. Excess N is released from microbial cells as ammonium (N mineralization), which in turn can serve as substrate for nitrification. According to stoichiometric theory, N mineralization and nitrification are expected to increase in relation to protein depolymerization with decreasing N limitation, and thus from higher to lower latitudes and from topsoils to subsoils. To test these hypotheses, we compared gross rates of protein depolymerization, N mineralization and nitrification (determined using N-15 pool dilution assays) in organic topsoil, mineral topsoil, and mineral subsoil of seven ecosystems along a latitudinal transect in western Siberia, from tundra (67 degrees N) to steppe (54 degrees N). The investigated ecosystems differed strongly in N transformation rates, with highest protein depolymerization and N mineralization rates in middle and southern taiga. All N transformation rates decreased with soil depth following the decrease in organic matter content. Related to protein depolymerization, N mineralization and nitrification were significantly higher in mineral than in organic horizons, supporting a decrease in microbial N limitation with depth. In contrast, we did not find indications for a decrease in microbial N limitation from arctic to temperate ecosystems along the transect. Our findings thus challenge the perception of ubiquitous N limitation at high latitudes, but suggest a transition from N to C limitation of microorganisms with soil depth, even in high-latitude systems such as tundra and boreal forest.

Avaliação do desempenho do aço D6 tratado termicamente e netretado em plasma com gaiola catódica visando aplicação industrial

In this research there was an evaluation of the best conditions of nitriding in plasma within a cathodic cage at an atmosphere of 80% N2-20%H2 in samples of tool manganese steel AISI D6, cold working, treated thermally in the following conditions: tension relief, treated thermally to temperature of maximum heat, temperate heat and temperate and temperate heat. A pressure of 2.5mbar and temperatures of 400 and 300ºC com treatment time of two and three hours were used to evaluate its performance as cutting tool (punch) of bicycle backs. Hardness, micro-structural aspects (layer thickness, interface, grain size etc), and crystal phases on the surface were appraised. When treated to tension relief, thermally treated to maximum heat temperature, temperature and temperate heat, the samples presented hardness levels of 243HV, 231HV, 832HV, and 653HV, respectively. The best nitrification conditions were: four hours and 300ºC for heat samples. A superficial hardness of 1000HV and a 108µm thickness for the nitrided layer were found in these samples

Release of available nitrogen from river-discharged dissolved organic matter by heterotrophic bacteria associated with the cyanobacterium Microcystis aeruginosa

The use of riverine dissolved organic matter by the heterotrophic bacteria associated with a culture of the cyanobacterium Microcystis aeruginosa and release of simple nitrogen compounds were studied in an experimental series. Bacteria reduced the bulk of dissolved organic nitrogen (DON) by half, but when associated with M. aeruginosa, DON was excreted and its concentration rose by 13%. During the stationary growth phase bacteria released ammonium, doubling the concentration of ammonia as well as of nitrates. Bacteria associated with M. aeruginosa consumed riverine DON and joined the ammonification and nitrification process, supplying cyanobacteria with simple nitrogen compounds.

Modeling nitrous oxide emissions in grass and grass-legume pastures in the western Brazilian Amazon.

Mineral nitrogen (N) dynamics in soil and the exchange of N gaseous in the interface soil-atmosphere are intimately associated with animal manure in pastures. According to soil inorganic-N pools and the site studied, forest or pasture, and pastures age the soil inorganic-N pools of ammonium and nitrate can be similar in the forest or ammonium dominated in the pasture. Also annual average net nitrification rates at soil surface in forest can be higher than in pasture suggesting a higher potential for nitrate-N losses either through leaching or gaseous emissions from intact forests compared with established pastures (NEILL et al., 1995).