Nitrogen-15 and Oxygen-18 Natural Abundance of Potassium Chloride Extractable Soil Nitrate Using the Denitrifier Method

In agroecosystems, most isotopic investigations of NO3- involve the use of tracers that are artificially enriched in 15N. Although the dual isotope composition of NO3-— d15N and d18O is especially beneficial for understanding the origin and fate of NO3-, its use for KCl-extractable soil NO3- has been hampered by the lack of a suitable analytical technique. Our objective was to test whether the denitrifier method, whereby NO3- is reduced to N2O before mass spectrometric analysis, can be used to determine the N and O isotopic composition of NO3- from 2 M KCl soil extracts. Several internationally accepted NO3- standards were dissolved in 2 M KCl, the conventional extractant for soil inorganic N, and inoculated with the bacterial strain Pseudomonas aureofaciens (ATCC no. 13985). The standard deviation of the NO3- standards analyzed did not exceed 0.2‰ for d15N and 0.3‰ for d18O values. After appropriate corrections, differences between our measured and consensus d15N and d18O values of standard NO3- generally were within the standard deviations given for the consensus values. Both d15N and d18O values were reproducible among separate analytical runs. The method was also tested on genuine 2 M KCl extracts from unfertilized and fertilized soils. Depending on N fertilization, the soils had distinct d15N and d18O values, which were attributed to amendment with NH4NO3 fertilizer. Hence, our data indicate that the denitrifier method provides a fast, reliable, precise, and accurate way of simultaneously analyzing the natural abundances of 15N and 18O in KCl-extractable soil NO3-.

Tracing nitrate and sulfate in river basins using isotope techniques

The objective of this paper is to outline how stable isotope techniques can contribute to the elucidation of the sources and the fate of riverine nitrate and sulphate in watershed studies. The example used is the Oldman River Basin (OMRB), located in southern Alberta (Canada). Increasing sulphate concentrations and decreasing d34S values along the flowpath of the Oldman River indicate that oxidation of pyrite in tills is a major source of riverine sulphate in the agriculturally used portion of the OMRB. Chemical and isotopic data showed that manure-derived nitrogen contributes significantly to the increase in nitrate concentrations in the Oldman River and its tributaries draining agricultural land. It is suggested that hydrological conditions control agricultural return flows to the surface water bodies in southern Alberta and impart significant seasonal variations on concentrations and isotopic compositions of riverine nitrate. Combining isotopic, chemical, and hydrometric data permitted us to estimate the relative contribution of major sources to the total solute fluxes. Hence, we submit that isotopic measurements can make an important contribution to the identification of nutrient and pollutant sources and to river basin management.

Isotopic Assessment of Sources of Surface Water Nitrate within the Oldman River Basin, Southern Alberta, Canada

Concentrations and isotopic compositions of NO-3 from the Oldman River (OMR) and some of its tributaries (Alberta, Canada) have been determined on a monthly basis since December 2000 to assess temporal and spatial variations of riverine NO-3 sources within the OMR basin. For the OMR sites, NO-3 -N concentrations reached up to 0.34 mg L-1, d15N-NO-3 values varied between –0.3 and +13.8‰, and d18O-NO-3 values ranged from –10.0 to +5.7‰. For the tributary sites, NO-3 -N concentrations were as high as 8.81 mg L-1, d15N-NO-3 values varied between –2.5 and +23.4‰, and d18O-NO-3 values ranged from –15.2 to +3.4‰. Tributaries in the western, relatively pristine forested part of the watershed add predominantly NO-3 to the OMR with d15N-NO-3 indicative of soil nitrification. In contrast, tributaries in the eastern agriculturally-urban-industrially-used part of the basin contribute NO-3 with d15N-NO-3 values of about +16‰ indicative of manure and/or sewage derived NO-3. This difference in d15N-NO-3 values of tributaries was found to be independent of the season, but rather indicates a spatial change in the NO-3 source, which correlates with land use changes within the OMR basin. As a consequence of tributary influx, d15N-NO-3 values in the Oldman River increased from +6‰ in the downstream direction (W to E), although [NO-3 -N] increased only moderately (generally

Isotopic assessment of sources and processes affecting sulfate and nitrate in surface water and groundwater of Luxembourg

Surface water and deep and shallow groundwater samples were taken from selected parts of the Grand-Duchy of Luxembourg to determine the isotopic composition of nitrate and sulfate, in order to identify sources and/or processes affecting these solutes. Deep groundwater had sulfate concentrations between 20 and 40 mg/L, d34Ssulfate values between -3.0 and -20.0‰, and d18Osulfate values between +1.5 and +5.0‰; nitrate was characterized by concentrations varying between

Distinct patterns of nitrate reductase activity in brown algae: Light and ammonium sensitivity in Laminaria digitata is absent in Fucus species

Fucus and Laminaria species, dominant seaweeds in the intertidal and subtidal zones of the temperate North Atlantic, experience tidal cycles that are not synchronized with light:dark (L:D) cycles. To investigate how nutrient assimilation is affected by light cycles, the activity of nitrate reductase (NR) was examined in thalli incubated in outdoor tanks with flowing seawater and natural L:D cycles. NR activity in Laminaria digitata (Huds.) Lamour. showed strong diel patterns with low activities in darkness and peak activities near midday. This diel pattern was controlled by light but not by a circadian rhythm. In contrast, there was no diel variation in NR activity in Fucus serratus L., F. vesiculosus (L.) Lamour., and F. spiralis L. either collected directly from the shore or maintained in the outdoor tanks. In laboratory cultures, transfer to continuous darkness suppressed NR activity in L. digitata, but not in F. vesiculosus; continuous light increased NR activity in L. digitata but decreased activity in F. vesiculosus. Furthermore, 4 d enrichment with ammonium (50 mu mol . L-1 pulses), resulted in NR activity declining by > 80% in L. digitata, but no significant changes in F. serratus. Seasonal differences in maximum NR activity were present in both genera with activities highest in late winter and lowest in summer. This is the first report of NR activity in any alga that is not strongly regulated by light and ammonium. Because light and tidal emersion do not always coincide, Fucus species may have lost the regulation of NR by light that has been observed in other algae and higher plants.

The electrochemical oxidation and reduction of nitrate ions in the room temperature ionic liquid [C(2)mim][NTf2]; the latter behaves as a 'melt' rather than an 'organic solvent'

The electrochemical oxidation of 1-butyl-3-methylimidazolium nitrate [C(4)mim][NO3] was studied by cyclic voltammetry in the room temperature ionic liquid (RTIL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [C(2)mim][NTf2]. A sharp peak was observed on a Pt microelectrode (d = 10 mu m), and a diffusion coefficient at infinite dilution of ca. 2.0 x 10(-11) m(2) s(-1) was obtained. Next, the cyclic voltammetry of sodium nitrate (NaNO3) and potassium nitrate (KNO3) was studied, by dissolving small amounts of solid into the RTIL [ C2mim][ NTf2]. Similar oxidation peaks were observed, revealing diffusion coefficients of ca. 8.8 and 9.0 x 10(-12) m(2) s(-1) and solubilities of 11.9 and 10.8 mM for NaNO3 and KNO3, respectively. The smaller diffusion coefficients for NaNO3 and KNO3 (compared to [C(4)mim][NO3]) may indicate that NO3- is ion-paired with Na+ or K+. This work may have applications in the electroanalytical determination of nitrate in RTIL solutions. Furthermore, a reduction feature was observed for both NaNO3 and KNO3, with additional anodic peaks indicating the formation of oxides, peroxides, superoxides and nitrites. This behaviour is surprisingly similar to that obtained from melts of NaNO3 and KNO3 at high temperatures ( ca. 350 - 500 degrees C), and this observation could significantly simplify experimental conditions required to investigate these compounds. We then used X-ray photoelectron spectroscopy (XPS) to suggest that disodium( I) oxide (Na2O), which has found use as a storage compound for hydrogen, was deposited on a Pt electrode surface following the reduction of NaNO3.

Mercurous dimethylglyoximato nitrate, Hg-2(Dmg)(2)(NO3)(2)

Colourless needles of mercurous dimethylglyoximato nitrate, Hg-2(Dmg)(2)(NO3)(2), grow from a diluted nitric acid solution of mercurous nitrate and dimethylglyoxime. The crystal structure (triclinic, P (1) over bar, a = 728.50(13), b = 1066.8(2), c = 1167.9(2) pm, alpha = 93.78(2)degrees, beta = 94.16(2)degrees, gamma = 98.61(2)degrees, R-all = 0,0726) contains the cations [Hg-2(Dmg)(2)](2+) and

Ammonium mercury(II) dichloride nitrate, (NH4)(2)HgCl2(NO3)(2)

The title compound, (NH4)(2)HgCl2 (NO3)(2), is a double salt of HgCl2 and NH4NO3 and can also be written as `HgCl2.2NH(4)NO(3)'. The structure contains HgCl2 units which are connected by nitrate groups, through long links of ca. 2.90 Angstrom, to give chains running along [010]. All atoms apart from the two oxygen atoms are located on a mirror plane perpendicular to the b axis. The coordination around mercury is a distorted hexagonal bipyramid.