Comparison of isotope pairing and N2:Ar methods for measuring sediment denitrification—Assumption, modifications, and implications

Denitrification has been measured during the last few years using two different methods in particular: isotope pairing measured on a triple-collector isotopic ratio mass spectrometer and N₂:Ar ratios measured on a membrane inlet mass spectrometer (MIMS). This study compares these two techniques in short-term batch experiments. Rates obtained using the original N₂∶Ar method were up to 3 to 4 times higher than rates obtained using the isotope pairing technique due to O₂ reacting with the N₂ during MIMS analysis. Oxygen combines with N₂ within the mass spectrometer ion source forming NO⁺ which reduces the N₂ concentration. The decrease in N₂ is least at lower O₂ concentrations and since oxygen is typically consumed during incubations of sediment cores, the result is often a pseudo-increase in N₂ concentration being interpreted as denitrification activity. The magnitude of this ocygen effect may be instrument specific. The reaction of O₂ with N₂ and the subsequent decrease in N₂ was only partly correctly using an O₂ correction curve for the relationship between N₂ and O₂ concentrations. The O₂ corrected N₂∶Ar denitrification rates were lower, but still did not match the isotope pairing rates and the variability between replicates was much higher. Using a copper reduction column heated to 600°C to remove all of the O₂ from the sample before MIMS analysis resulted in comparable rates (slightly lower), and comparable variability between replicates, to the isotope pairing technique. The N₂:Ar technique determines the net N₂ production as the difference between N₂ production by denitrification and N₂ consumption by N-fixation, while N-fixation has little effect on the isotope pairing technique which determines a rate very close to the gross N₂ production. When the two different techniques were applied on the same sediment, the small difference in rates obtained by the two methods seemed to reflect N-fixation as also supported from measurements of ethylene production in acetylene enriched sediment cores. The N₂:Ar and isotope pairing techniques may be combined to provide simultaneous measurements of denitrification and N-fixation. Both techniques have several assumptions that must be met to achieve accurate rates; a number of tests are outlined that can be applied to demonstrate that these assumptions are being meet.     

Phytoplankton, nutrients, and transparency in Danish coastal waters

We present a comparative analysis of 1400 data series of water chemistry (particularly nitrogen and phosphorus concentrations), phytoplankton biomass as chlorophylla (chla) concentrations, concentrations of suspended matter and Secchi depth transparency collected from the mid-1980s to the mid-1990s from 162 stations in 27 Danish fjords and coastal waters. The results demonstrate that Danish coastal waters were heavily eutrophied and had high particle concentrations and turbid waters. Median values were 5.1 μg chla 1⁻¹, 10.0 mg DW 1⁻¹ of suspended particles, and Secchi depth of 3.6 m. Chlorophyll concentration was strongly linked to the total-nitrogen concentration. The strength of this relationship increased from spring to summer as the concentration of total nitrogen declined. During summer, total nitrogen concentrations accounted for about 60% of the variability in chlorophyll concentrations among the different coastal systems. The relationship between chlorophyll and total phosphorus was more consistant over the year and correlations were much weaker than encountered for total nitrogen. Secchi depth could be predicted with good precision from measurements of chlorophyll and suspended matter. In a multiple stepwise regression model with In-transformed values the two variables accounted for most of the variability in water transparency for the different seasons and the period March–October as a whole (c. 80%). We were able to demonstrate a significant relationship between total nitrogen and Secchi depth, with important implications for management purposes.     

Palaeolimnology of Lake Piene-Kuuppalanlampi (Kurkijoki, Karelian Republic, Russia): isolation history, lake ecosystem development and long-term agricultural impact

The post-glacial history of Lake Pieni-Kuuppalanlampi, western Lake Ladoga region, was studied by means of stratigraphic pollen and diatom analyses. Diatoms were analysed to track the isolation history of the basin and the limnological effects of the early land-use phases indicated by pollen analysis. Chrysophycean stomatocysts and Isoëtes spores were also employed in the limnological reconstructions. Sediment dating was provided by six conventional radiocarbon dates.The lower part of the 370-cm long sediment sequence represents early Holocene, large lake conditions: the (freshwater) Yoldia and Ancylus stages of the Baltic basin, with a short-term lagoonal or isolation phase at the end of Yoldia. The basin was isolated due to Ancylus lake regression at 9785 cal B.P. For the small-lake sequence (0–250 cm) we used diatom inferences (WA-method) for hindcasting water chemistry. The post-isolation limnology of Pieni-Kuuppalanlampi reflects the development of vegetation on its small hill-top catchment. In its early development, the lake was mesotrophic, but became more acidic (pH about 6) and oligotrophic after the decline of temperate hardwood trees and the spread of spruce to the area after around 5000 B.P. The lake ecosystem appears to have reacted sensitively to agricultural land-use in the catchment from AD 400–800 onwards: inferred total phosphorus levels and pH both rise during these periods.     

An Mw based earthquake Catalogue for central, northern and northwestern Europe using a hierarchy of magnitude conversions

Data from 25 local catalogues and 30special studies of earthquakes in central,northern and northwestern Europe have beenincorporated into a Databank. The dataprocessing includes discriminating eventtypes, eliminating fake events and dupletsand converting different magnitudes andintensities to M_w if this is not givenby the original source. The magnitudeconversion is a key task of the study andimplies establishment of regressionequations where no local relations exist.The Catalogue contains tectonic events fromthe Databank within the area44°N–72°N,25°W–32°E and the time period1300–1993. The lower magnitude level forthe Catalogue entries is setat M_w == 3.50. The area covered by thedifferent catalogues are associated withpolygons. Within each polygon only datafrom one or a small number of the localcatalogues, supplemented by data fromspecial studies, enter the Catalogue. Ifthere are two or more such catalogues orstudies providing a solution for an event,a priority algorithm selects one entry forthe Catalogue. Then M_w is calculatedfrom one of the magnitude types, or frommacroseismic data, given by the selectedentry according to another priority scheme.The origin time, location, M_w magnitude and reference are specified for eachentry of the Catalogue. So is theepicentral intensity, I₀, if providedby the original source. Following thesecriteria, a total of about 5,000earthquakes constitute the Catalogue.Although originally derived for the purposeof seismic hazard calculation within GSHAP,the Catalogue provides a data base for manytypes of seismicity and seismic hazardstudies.     

First-Order Chemistry in the Surface-Flux Layer

We have discussed the behavior of a non-conserved scalar in the stationary, horizontally homogeneous, neutral surface-flux layer and, on the basis of conventional second-order closure, derived analytic expressions for flux and for mean concentration of a gas, subjected to a first-order removal process. The analytic flux solution showed a clear deviation from the constant flux, characterizing a conserved scalar in the surface-flux layer. It decreases with height and is reduced by an order of magnitude of the surface flux at a height equal to about the typical mean distance a molecule can travel before destruction. The predicted mean concentration profile, however, shows only a small deviation from the logarithmic behavior of a conserved scalar. The solution is consistent with assuming a flux-gradient relationship with a turbulent diffusivity corrected by the Damköhler ratio, the ratio of a characteristic turbulent time scale and the scalar mean lifetime. We show that if we use only first-order closure and neglect the effect of the Damköhler ratio on the turbulent diffusivity we obtain another analytic solution for the profiles of the flux and the mean concentration which, from an experimental point of view, is indistinguishable from the first analytic solution. We have discussed two cases where the model should apply, namely NO which, by night, is irreversibly destroyed by interaction with mainly O₃ and the radioactive ²²⁰Rn. Only in the last case was it possible to find data to shed light on the validity of our predictions. The agreement seemed such that a falsification of our model was impossible. It is shown how the model can be used to predict the surface flux of ²²⁰Rn from measured concentration profiles.     

Stratigraphy of the upper cretaceous and lower tertiary strata in the Tethyan Himalayas of Tibet (Tingri area,China)

The 1500-m-thick marine strata of the Tethys Himalaya of the Zhepure Mountain (Tingri, Tibet) comprise the Upper Albian to Eocene and represent the sedimentary development of the passive northern continental margin of the Indian plate. Investigations of foraminifera have led to a detailed biozonation which is compared with the west Tethyan record. Five stratigraphic units can be distinguished: The Gamba group (Upper Albian - Lower Santonian) represents the development from a basin and slope to an outer-shelf environment. In the following Zhepure Shanbei formation (Lower Santonian - Middle Maastrichtian), outer-shelf deposits continue. Pebbles in the top layers point to beginning redeposition on a continental slope. Intensified redeposition continues within the Zhepure Shanpo formation (Middle Maastrichtian - Lower Paleocene). The series is capped by sandstones of the Jidula formation (Danian) deposited from a seaward prograding delta plain. The overall succession of these units represents a sea-level high at the Cenomanian/Turonian boundary followed, from the Turonian to Danian, by an overall shallowing-upward megasequence. This is followed by a final transgression — regression cycle during the Paleocene and Eocene, documented in the Zhepure Shan formation (?Upper Danian - Lutetian) and by Upper Eocene continental deposits. The section represents the narrowing and closure of the Tethys as a result of the convergence between northward-drifting India and Eurasia. The plate collision started in the Lower Maastrichtian and caused rapid changes in sedimentation patterns affected by tectonic subsidence and uplift. Stronger subsidence and deposition took place from the Middle Maastrichtian to the Lower Paleocene. The final closure of remnant Tethys in the Tingri area took place in the Lutetian.     

Simulation of normal distributed smooth fields by Karhunen-Loéve expansion in combination with kriging

Simulation of multigaussian stochastic fields can be made after a Karhunen-Loéve expansion of a given covariance function. This method is also called simulation by Empirical Orthogonal Functions. The simulations are made by drawing stochastic coefficients from a random generator. These numbers are multiplied with eigenfunctions and eigenvalues derived from the predefined covariance model. The number of eigenfunctions necessary to reproduce the stochastic process within a predefined variance error, turns out to be a cardinal question. Some ordinary analytical covariance functions are used to evaluate how quickly the series of eigenfunctions can be truncated. This analysis demonstrates extremely quick convergence to 99.5% of total variance for the 2nd order exponential (‘gaussian’) covariance function, while the opposite is true for the 1st order exponential covariance function. Due to these convergence characteristics, the Karhunen-Loéve method is most suitable for simulating smooth fields with ‘gaussian’ shaped covariance functions. Practical applications of Karhunen-Loéve simulations can be improved by spatial interpolation of the eigenfunctions. In this paper, we suggest interpolation by kriging and limits for reproduction of the predefined covariance functions are evaluated.     

Effet du vieillissement des céramiques poreuses sur leur capacité à évaluer la concentration de pesticide en solution

The soil solution sampling by ceramic cups allows pesticide transfer monitoring in the soil during long times. The ageing of material involves a bias in the sampling results. In laboratory, the comparison of two types of ceramic suction cups, new and installed in situ during four years, shows a modification of the hydrodynamic properties and a possible evolution of the adsorption capacity of the matrix. The passage rate, as well qualitative as quantitative, is better for the old material. Recommendations about site management are finally exposed. To cite this article: N. Domange et al., C. R. Geoscience 336 (2004).