Nitrite consumption and associated isotope changes during a river flood event in the Elbe river

In oceans, estuaries, and rivers, nitrification is an important nitrate source, and stable isotopes of nitrate are often used to investigate recycling processes (e.g. remineralisation, nitrification) in the water column. Nitrification is a two-step process, where ammonia is oxidised via nitrite to nitrate. Nitrite usually does not accumulate in natural environments, which makes it difficult to study the single isotope effect of ammonia oxidation or nitrite oxidation in natural systems. However, during an exceptional flood in the Elbe River in June 2013, we found a unique co-occurrence of ammonium, nitrite, and nitrate in the water column, returning towards normal summer conditions within 1 week. Over the course of the flood, we analysed the evolution of d15N-[NH4]+ and d15N-[NO2]- in the Elbe River. In concert with changes in suspended particulate matter (SPM) and d15N SPM, as well as nitrate concentration, d15N-NO3 - and d18O-[NO3] -, we calculated apparent isotope effects during net nitrite and nitrate consumption. During the flood event, > 97 % of total reactive nitrogen was nitrate, which was leached from the catchment area and appeared to be subject to assimilation. Ammonium and nitrite concentrations increased to 3.4 and 4.4 µmol/l, respectively, likely due to remineralisation, nitrification, and denitrification in the water column. d15N-[NH4]+ values increased up to 12 per mil, and d15N-[NO2]- ranged from -8.0 to -14.2 per mil. Based on this, we calculated an apparent isotope effect 15-epsilon of -10.0 ± 0.1 per mil during net nitrite consumption, as well as an isotope effect 15-epsilon of -4.0 ± 0.1 per mil and 18-epsilon of -5.3 ± 0.1 per mil during net nitrate consumption. On the basis of the observed nitrite isotope changes, we evaluated different nitrite uptake processes in a simple box model. We found that a regime of combined riparian denitrification and 22 to 36 % nitrification fits best with measured data for the nitrite concentration decrease and isotope increase.

Soil properties and microbial indicators of samples from Lake Wellman, Darwin Mountains, Antarctica

Four pedons on each of four drift sheets in the Lake Wellman area of the Darwin Mountains were sampled for chemical and microbial analyses. The four drifts, Hatherton, Britannia, Danum, and Isca, ranged from early Holocene (10 ka) to mid-Quaternary (c. 900 ka). The soil properties of weathering stage, salt stage, and depths of staining, visible salts, ghosts, and coherence increase with drift age. The landforms contain primarily high-centred polygons with windblown snow in the troughs. The soils are dominantly complexes of Typic Haplorthels and Typic Haploturbels. The soils were dry and alkaline with low levels of organic carbon, nitrogen and phosphorus. Electrical conductivity was high accompanied by high levels of water soluble anions and cations (especially calcium and sulphate in older soils). Soil microbial biomass, measured as phospholipid fatty acids, and numbers of culturable heterotrophic microbes, were low, with highest levels detected in less developed soils from the Hatherton drift. The microbial community structure of the Hatherton soil also differed from that of the Britannia, Danum and Isca soils. Ordination revealed the soil microbial community structure was influenced by soil development and organic carbon.

(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.

Seawater carbonate chemistry and biological processes of Emiliania huxleyi (PML B92/11) during experiments, 2011

The present study investigates the combined effect of phosphorous limitation, elevated partial pressure of CO2 (pCO2) and temperature on a calcifying strain of Emiliania huxleyi (PML B92/11) by means of a fully controlled continuous culture facility. Two levels of phosphorous limitation were consecutively applied by renewal of culture media (N:P = 26) at dilution rates (D) of 0.3 d- and 0.1 d-1. CO2 and temperature conditions were 300, 550 and 900 µatm pCO2 at 14 °C and 900 µatm pCO2 at 18 °C. In general, the steady state cell density and particulate organic carbon (POC) production increased with pCO2, yielding significantly higher concentrations in cultures grown at 900 µatm pCO2 compared to 300 and 550 µatm pCO2. At 900 µatm pCO2, elevation of temperature as expected for a greenhouse ocean, further increased cell densities and POC concentrations. In contrast to POC concentration, C-quotas (pmol C cell-1) were similar at D = 0.3 d-1 in all cultures. At D = 0.1 d-1, a reduction of C-quotas by up to 15% was observed in the 900 µatm pCO2 at 18 °C culture. As a result of growth rate reduction, POC:PON:POP ratios deviated strongly from the Redfield ratio, primarily due to an increase in POC. Ratios of particulate inorganic and organic carbon (PIC:POC) ranged from 0.14 to 0.18 at D = 0.3 d-1, and from 0.11 to 0.17 at D = 0.1 d-1, with variations primarily induced by the changes in POC. At D = 0.1 d-1, cell volume was reduced by up to 22% in cultures grown at 900 µatm pCO2. Our results indicate that changes in pCO2, temperature and phosphorus supply affect cell density, POC concentration and size of E. huxleyi (PML B92/11) to varying degrees, and will likely impact bloom development as well as biogeochemical cycling in a greenhouse ocean.

(Table T2) Biogenic opal in Palmer Deep sediments at ODP Site 178-1098

High-resolution records of sedimentary proxies provide insights into fine-scale geochemical responses to climatic forcing. Gamma-ray attenuation (GRA) bulk-density data and magnetic stratigraphy records from Palmer Deep, Site 1098, show variability close to the same scale as ice cores, making this site ideal for high-resolution geochemical investigations. In conjunction with shipboard geophysical measurements, silica records allow high-resolution evaluation of the frequencies and amplitudes of biogenic variability. This provides investigators additional data sets to evaluate the global extent of climatic events that are presently defined by regional oceanic data sets (e.g., Younger Dryas in the North Atlantic) and to evaluate the potential mechanisms that link biological productivity and climate in the Southern Ocean. In addition, because of the observed links between diatom blooms and export productivity (Michaels and Silver, 1988, doi:10.1016/0198-0149(88)90126-4), biogenic silica may be an indicator of the efficiency of the biological pump (removal of organic carbon from the euphotic zone and burial within the sediments). Because the net removal of CO2 (on short time scales up to millennial, the balance between upwelled CO2, carbon fixation, and the removal of organic carbon from the surface ocean) can determine the atmospheric concentration; proxies that allow us to quantify export production yield insights into carbon cycle responses. In today's ocean, diatoms are integrally linked with new production (production based on the use of nitrate and molecular nitrogen rather than ammonium, which is generated by the microbial degradation of organic carbon) (Dugdale and Goering, 1967). Thus, as with nutrient utilization proxies, biogenic silica may be a good indicator of export production. The difficulties lie in translating the biogenic opal burial records to export production. Numerous factors control the preservation of sedimentary biogenic silica, including depth of the water column, water temperature, trace element chemistry, grazing pressure, bloom structure, and species composition of the diatom assemblage (Nelson et al., 1995, doi:10.1029/95GB01070). In addition, several recent investigations have noted additional complications. Iron limitation increases the uptake of Si relative to carbon (Hutchins et al., 1998, ; Takeda, 1998, doi:10.1038/31674). In the Southern Ocean, iron limitation could produce more robust, and thus better preserved, diatoms; thus, the burial record may be a record of iron limitation rather than of the export of organic carbon (Boyle, 1998). In addition, laboratory experiments show that bacteria accelerate the dissolution of biogenic silica (Bidle and Azam, 1999, doi:10.1038/17351). Both the species composition and temperature seem to influence the amount of dissolution. Evidence of recycling of silicic acid within the photic zone (Brzezinski et al., 1997) suggests that the silica pump (removal from the euphotic zone of silica relative to nitrogen and phosphorus) may work with variable efficiency. This becomes an issue when trying to reconstruct the removal of organic carbon from sedimentary biogenic silica records. In fact, there is a wide range in the Si:Corganic molar ratio in the Southern Ocean (0.18-0.81) (Nelson et al., 1995; Ragueneau et al., 2000, doi:10.1016/S0921-8181(00)00052-7). Thus, the presence (or absence) of biogenic silica alone may tell us little about the export productivity, complicating the interpretation of age-related trends. One recent assessment has added some hope to links between productivity and opal burial in the Southern Ocean (Pondaven et al., 2000). Quantitative comparison of different productivity proxies will greatly aid in this evaluation.