N2O concentration and isotope signature along profiles provide deeper insight into the fate of N2O in soils†

Nitrous oxide is an important greenhouse gas and its origin and fate are thus of broad interest. Most studies on emissions of nitrous oxide from soils focused on fluxes between soil and atmosphere and hence represent an integration of physical and biological processes at different depths of a soil profile. Analysis of N₂O concentration and isotope signature along soil profiles was suggested to improve the localisation of sources and sinks in soils as well as underlying processes and could therefore extend our knowledge on processes affecting surface N₂O fluxes. Such a mechanistic understanding would be desirable to improve N₂O mitigation strategies and global N₂O budgets. To investigate N₂O dynamics within soil profiles of two contrasting (semi)natural ecosystem types (a temperate acidic fen and a Norway spruce forest), soil gas samplers were constructed to meet the different requirements of a water-saturated and an unsaturated soil, respectively. The samplers were installed in three replicates and allowed soil gas sampling from six different soil depths. We analysed soil air for N₂O concentration and isotope composition and calculated N₂O net turnover using a mass balance approach and considering diffusive fluxes. At the fen site, N₂O was mainly produced in 30–50 cm soil depth. Diffusion to adjacent layers above and below indicated N₂O consumption. Values of δ¹⁵N and δ¹⁸O of N₂O in the fen soil were always linearly correlated and their qualitative changes within the profile corresponded with the calculated turnover processes, suggesting further reduction of N₂O. In the spruce forest, highest N₂O production occurred in the topsoil, but there was also notable production occurring in the subsoil at a depth of 70 cm. Changes in N₂O isotope composition as to be expected from local production and consumption processes within the soil profile did hardly occur, though. This was presumably caused by high diffusive fluxes and comparatively low net turnover, as isotope signatures approached values measured for ambient N₂O towards the topsoil. Our results demonstrate a highly variable influence of diffusive versus production/consumption processes on N₂O concentration and isotope composition, depending on the type of ecosystem. This finding indicates the necessity of further N₂O concentration and isotope profile investigations in different types of natural and anthropogenic ecosystems in order to generalise our mechanistic understanding of N₂O exchange between soil and atmosphere.     

Oxygen and nitrogen isotopic composition of nitrate in commercial fertilizers,nitric acid,and reagent salts

Nitrate is a key component of synthetic fertilizers that can be beneficial to crop production in agro-ecosystems, but can also cause damage to natural ecosystems if it is exported in large amounts. Stable isotopes, both oxygen and nitrogen, have been used to trace the sources and fate of nitrate in various ecosystems. However, the oxygen isotope composition of synthetic and organic nitrates is poorly constrained. Here, we present a study on the N and O isotope composition of nitrate-based fertilizers. The δ¹⁵N values of synthetic and natural nitrates were 0?±?2?‰ similar to the air N₂ from which they are derived. The δ¹⁸O values of synthetic nitrates were 23?±?3?‰, similar to air O₂, and natural nitrate fertilizer δ¹⁸O values (55?±?5?‰) were similar to those observed in atmospheric nitrate. The Δ¹⁷O values of synthetic fertilizer nitrate were approximately zero following a mass-dependent isotope relationship, while natural nitrate fertilizers had Δ¹⁷O values of 18?±?2?‰ similar to nitrate produced photochemically in the atmosphere. These narrow ranges of values can be used to assess the amount of nitrate arising from fertilizers in mixed systems where more than one nitrate source exists (soil, rivers, and lakes) using simple isotope mixing models.     

Analysis of the coexisting pathways for NO and N2O formation in Chernozem using the 15N-tracer SimKIM-Advanced model

The nitrogen (N) cycle consists of a variety of microbial processes. These processes often occur simultaneously in soils, but respond differently to local environmental conditions due to process-specific biochemical restrictions (e.g. oxygen levels). Hence, soil nitrogen cycling (e.g. soil N gas production through nitrification and denitrification) is individually affected through these processes, resulting in the complex and highly dynamic behaviour of total soil N turnover. The development and application of methods that facilitate the quantification of individual contributions of coexisting processes is a fundamental prerequisite for (i) understanding the dynamics of soil N turnover and (ii) implementing these processes in ecosystem models. To explain the unexpected results of the triplet tracer experiment (TTE) of Russow et al. (Role of nitrite and nitric oxide in the processes of nitrification and denitrification in soil: results from ¹⁵N tracer experiments. Soil Biol Biochem. 2009;41:785–795) the existing SimKIM model was extended to the SimKIM-Advanced model through the addition of three separate nitrite subpools associated with ammonia oxidation, oxidation of organic nitrogen (N_org), and denitrification, respectively. For the TTE, individual treatments with ¹⁵N ammonium, ¹⁵N nitrate, and ¹⁵N nitrite were conducted under oxic, hypoxic, and anoxic conditions, respectively, to clarify the role of nitric oxide as a denitrification intermediate during N₂O formation. Using a split nitrite pool, this analysis model explains the observed differences in the ¹⁵N enrichments in nitric oxide (NO) and nitrous oxide (N₂O) which occurred in dependence on different oxygen concentrations. The change from oxic over hypoxic to anoxic conditions only marginally increased the NO and N₂O release rates (1.3-fold). The analysis using the model revealed that, under oxic and hypoxic conditions, N_org-based N₂O production was the dominant pathway, contributing to 90 and 50 % of the total soil N₂O release. Under anoxic conditions, denitrification was the dominant process for soil N₂O release. The relative contribution of N_org to the total soil NO release was small. Ammonia oxidation served as the major pathway of soil NO release under oxic and hypoxic conditions, while denitrification was dominant under anoxic conditions. The model parameters for soil with moderate soil organic matter (SOM) content were not scalable to an additional data set for soil with higher SOM content, indicating a strong influence of SOM content on microbial N turnover. Thus, parameter estimation had to be re-calculated for these conditions, highlighting the necessity of individual soil-dependent parameter estimations.     

Stable water isotope patterns in a climate change hotspot: the isotope hydrology framework of Corsica (western Mediterranean)

The Mediterranean is regarded as a region of intense climate change. To better understand future climate change, this area has been the target of several palaeoclimate studies which also studied stable isotope proxies that are directly linked to the stable isotope composition of water, such as tree rings, tooth enamel or speleothems. For such work, it is also essential to establish an isotope hydrology framework of the region of interest. Surface waters from streams and lakes as well as groundwater from springs on the island of Corsica were sampled between 2003 and 2009 for their oxygen and hydrogen isotope compositions. Isotope values from lake waters were enriched in heavier isotopes and define a local evaporation line (LEL). On the other hand, stream and spring waters reflect the isotope composition of local precipitation in the catchment. The intersection of the LEL and the linear fit of the spring and stream waters reflect the mean isotope composition of the annual precipitation (δ_P) with values of?8.6(±0.2) ‰ for δ¹⁸O and?58(±2) ‰ for δ²H. This value is also a good indicator of the average isotope composition of the local groundwater in the island. Surface water samples reflect the altitude isotope effect with a value of?0.17(±0.02) ‰ per 100 m elevation for oxygen isotopes. At Vizzavona Pass in central Corsica, water samples from two catchments within a lateral distance of only a few hundred metres showed unexpected but systematic differences in their stable isotope composition. At this specific location, the direction of exposure seems to be an important factor. The differences were likely caused by isotopic enrichment during recharge in warm weather conditions in south-exposed valley flanks compared to the opposite, north-exposed valley flanks.     

Natural abundances of 15N and 13C in leaves of some N2-fixing and non-N2-fixing trees and shrubs in Syria

A survey study was conducted on man-made plantations located at two different areas in the arid region of Syria to determine the variations in natural abundances of the ¹⁵N and ¹³C isotopes in leaves of several woody legume and non-legume species, and to better understand the consequence of such variations on nitrogen fixation and carbon assimilation. In the first study area (non-saline soil), the δ¹⁵N values in four legume species (Acacia cyanophylla,?1.73 ‰ Acacia farnesiana,?0.55 ‰ Prosopis juliflora,?1.64 ‰; and Medicago arborea,+1.6 \textperthousand) and one actinorhizal plant (Elaeagnus angustifolia,?0.46 to?2.1 ‰) were found to be close to that of the atmospheric value pointing to a major contribution of N₂ fixing in these species; whereas, δ¹⁵N values of the non-fixing plant species were highly positive. δ¹³C ‰; in leaves of the C3 plants were found to be affected by plant species, ranging from a minimum of?28.67 ‰; to a maximum of?23 ‰. However, they were relatively similar within each plant species although they were grown at different sites. In the second study area (salt affected soil), a higher carbon discrimination value (Δ¹³C ‰) was exhibited by P. juliflora, indicating that the latter is a salt tolerant species; however, its δ¹⁵N was highly positive (+7.03 ‰) suggesting a negligible contribution of the fixed N₂. Hence, it was concluded that the enhancement of N₂ fixation might be achieved by selection of salt-tolerant Rhizobium strains.     

The effect of physical back-diffusion of 13CO2 tracer on the coupling between photosynthesis and soil CO2 efflux in grassland

Pulse labelling experiments provide a common tool to study short-term processes in the plant–soil system and investigate below-ground carbon allocation as well as the coupling of soil CO₂ efflux to photosynthesis. During the first hours after pulse labelling, the measured isotopic signal of soil CO₂ efflux is a combination of both physical tracer diffusion into and out of the soil as well as biological tracer release via root and microbial respiration. Neglecting physical back-diffusion can lead to misinterpretation regarding time lags between photosynthesis and soil CO₂ efflux in grassland or any ecosystem type where the above-ground plant parts cannot be labelled in gas-tight chambers separated from the soil. We studied the effects of physical ¹³CO₂ tracer back-diffusion in pulse labelling experiments in grassland, focusing on the isotopic signature of soil CO₂ efflux. Having accounted for back-diffusion, the estimated time lag for first tracer appearance in soil CO₂ efflux changed from 0 to 1.81±0.56 h (mean±SD) and the time lag for maximum tracer appearance from 2.67±0.39 to 9.63±3.32 h (mean±SD). Thus, time lags were considerably longer when physical tracer diffusion was considered. Using these time lags after accounting for physical back-diffusion, high nocturnal soil CO₂ efflux rates could be related to daytime rates of gross primary productivity (R²=0.84). Moreover, pronounced diurnal patterns in the δ¹³C of soil CO₂ efflux were found during the decline of the tracer over 3 weeks. Possible mechanisms include diurnal changes in the relative contributions of autotrophic and heterotrophic soil respiration as well as their respective δ¹³C values. Thus, after accounting for physical back-diffusion, we were able to quantify biological time lags in the coupling of photosynthesis and soil CO₂ efflux in grassland at the diurnal time scale.     

Estimation of microbial methane generation and oxidation rates in the municipal solid waste landfill of Kaluga city,Russia

Using a theoretical model and mass isotopic balance, biogas (methane and CO₂) released from buried products at their microbial degradation was analysed in the landfill of municipal and non-toxic industrial solid organic waste near Kaluga city, Russia. The landfill contains about 1.34×10⁶ tons of waste buried using a ‘sandwich technique’ (successive application of sand–clay and waste layers). The δ¹³C values of biogenic methane with respect to CO₂ were?56.8 (±2.5) ‰, whereas the δ¹³C of CO₂ peaked at+9.12‰ (+1.4±2.3‰ on average), reflecting a virtual fractionation of carbon isotopes in the course of bacterial CO₂ reduction at the landfill body. After passing through the aerated soil layers, methane was partially oxidised and characterised by δ¹³C in the range of?50.6 to?38.2‰, evidencing enrichment in ¹³C, while the released carbon dioxide had δ¹³C of?23.3 to?4.04‰, respectively. On the mass isotopic balance for the δ¹³C values, the methane production in the landfill anaerobic zone and the methane emitted through the aerated landfill surface to the atmosphere, the portion of methane oxidised by methanotrophic bacteria was calculated to be from 10 to 40% (averaged about 25%). According to the theoretical estimation and field measurements, the annual rate of methane production in the landfill reached about 2.9(±1.4)×10⁹ g C CH₄ yr^?1 or 5.3(±2.6)×10⁶ m³ CH₄ yr^?1. The average rates of methane production in the landfill and methane emission from landfill to the atmosphere are estimated as about 53 (±26) g C CH₄ m^?2 d^?1 (or 4 (±2) mol CH₄ m^?2 d^?1) and 33 (±12) g C CH₄ m^?2 d^?1 (or 2.7 (±1) mol CH₄ m^?2 d^?1), respectively. The calculated part of methane consumed by methanotrophic bacteria in the aerated part of the landfill was 13(±7) g C CH₄ m^?2 d^?1 (or 1.1(±0.6) mol CH₄ m^?2 d^?1) on average.     

Rapid isotopic analysis of trace gases at atmospheric levels

A method is reported allowing simultaneous isotopic analysis of N₂ and N₂O at atmospheric concentrations. A gas chromatograph fitted with a thermal conductivity detector and micro desorption trap was interfaced to an isotope ratio mass spectrometer (Tracer Mass, Europa Scientific, Crewe, UK). CO₂ and H₂O were chemically removed prior to the complete sorption of N₂O onto a zeolite bed. N₂ was chromatographically purified prior to isotopic analysis. The N₂O was thermally desorbed into a slow carrier stream (300 μL min^?1) prior to analysis at m/z 44, 45 and 46. Precision of measurement was 0.3663 ± 0.000013 and 0.365 ± 0.0025 Atom % ¹⁵N as N₂ and N₂O respectively. The method was then evaluated for a soil denitrification experiment.

Es wird über eine Methode zur simultanen Isotopenanalyse am N₂ und N₂O bei atmosphärischer Konzentration berichtet. Ein Gaschromatograph mit Wärmeleitfähigkeitsdetektor und Mikrodesorptionsfalle wurde an ein IRM-Massenspektrometer (Tracer Mass, Europa Scientific, Crewe, GB) angekoppelt. CO₂ und H₂O wurden vor der vollständigen Adsorption des N₂O auf einem Zeolit-Bett chemisch entfernt. Das N₂ wurde vor der Isotopenanalyse chromatographisch gereinigt. Vor der Analyse bei M/Z 44, 45 und 46 wurde das N₂O thermisch desorbiert und in einen langsamen Trägergasstrom (300 μl min^?1) gebracht. Die Meßgenauigkeit betrug 0,3663 ± 0,000013 At-% ¹⁵N für N₂ und 0,365 ± 0,0025 At.-% für N₂O. Die Methode wurde dann für ein Boden-Denitrifizierungsexperiment erprobt.     

Isotopic characteristics of meteoric waters in the Belgrade region

Abstract

The stable isotope composition of hydrogen (δ²H) and oxygen (δ¹⁸O) in monthly precipitation and river water (Sava River and Danube) samples in the Belgrade area gathered between 1992 and 2005 are determined. The local meteoric water line δ²H=7.8 (±0.2) δ¹⁸O+7.3(±1.6) (r ²=0.98, n=60, σ=0.52) for the whole period of observation is close to the global meteoric water line. The amount-weighted mean δ²H and δ¹⁸O values of precipitation were?65±27 ‰ and?9.4±3.4 ‰, respectively. Good correlation between δ¹⁸O values (r>rsim0.67) and ambient temperature and relative humidity was obtained. Stream-water data ranged from?94 to?60 ‰ for δ²H and from?11.0 to ～5.7 ‰ for δ¹⁸O with highly statistically significant difference (p>0.01) between the Sava River and the Danube. In addition, the isotopic compositions of local precipitation and adjacent river water at monitoring sites were compared. Obtained data will give an opportunity to improve the knowledge of mixing stream water and local groundwater, and assessment of potential groundwater risks and pressures in the Belgrade basin.     

Carbon and oxygen isotope working standards from C3 and C4 photosynthates

A preparation of organic working standards for the online measurement of ¹³C/¹²C and ¹⁸O/¹⁶O ratios in biological material is presented. The organic working standards are simple and inexpensive C₃ and C₄ carbohydrates (sugars or cellulose) from distinct geographic origin, including white sugar, toilet and XEROX papers from Switzerland, maize from Ivory Coast, cane sugar from Brazil, papyrus from Egypt, and the core of the stem of a Cyperus papyrus plant from Kenya. These photosynthetic products were compared with International Atomic Energy standards CH-3 and CH-6 and other calibration materials. The presented working standards cover a 15 ‰ range of ¹³C/¹²C ratios and 9 ‰ for ¹⁸O/¹⁶O, with a precision<±0.2 ‰ for n>10.     

Groundwater of the Crimean peninsula: a first systematic study using stable isotopes

ABSTRACT

Karst springs in the Main Range of the Crimean Mountains and the Crimean Piedmont show a restricted range of values (δ¹⁸O?=?–10.5 to –8.0 ‰, δ²H?=?–72 to –58 ‰), somewhat more negative than the weighted mean of meteoric precipitation. This suggests preferential recharge at higher elevations during winter months. Groundwater tapped by boreholes splits in three groups. A first group has isotopic properties similar to those of the springs. The second group shows significantly lower values (δ¹⁸O?=?–13.3 to –12.0 ‰, δ²H?=?–95 to –82 ‰), suggesting recharge during colder Pleistocene times. The third group has high isotope values (δ¹⁸O?=?–2.5 to +1.0 ‰, δ²H?=?–24 to –22 ‰); the data points are shifted to the right of the Local Meteoric Water Line, suggesting water–rock exchange processes in the aquifer. These boreholes are located in the Crimean Plains and discharge mineralized (ca. 25 g L^?1) thermal (65°C) water from a depth of 1600–1800 m. Groundwater associated with mud volcanoes on the Kerch peninsula have distinct isotope characteristics (δ¹⁸O?=?–1.6 to +9.4 ‰, δ²H?=?–30 to –18 ‰). Restricted δ²H variability along with variable and high δ¹⁸O values suggest water–rock interactions at temperatures exceeding 95 °C.     

Spring response to precipitation events using δ18O and δ2H in the Tanour catchment,NW Jordan

The Tanour spring is one of the several karst springs located in the northern part of Jordan. Water samples from the Tanour spring and precipitation were collected in the area of Ajloun in NW Jordan for the analysis of stable oxygen and hydrogen isotopes to evaluate the spring response to precipitation events. Rainwater and snow samples were collected from different elevations during winters of 2013–2014 and 2014–2015. In addition, spring samples were collected between December 2014 and March 2015. δ¹⁸O values in rainwater vary from ?3.26 to ?17.34?‰ (average: ?7.84?±?3.23?‰), while δ²H values range between ?4.4 and ?110.4?‰ (average: ?35.7?±?25.0?‰). Deuterium excess ranges from 17.8 to 34.1?‰ (average: 27.1?±?4.0?‰). The Local Meteoric Water Line for the study area was calculated to be δ²H?=?7.66*δ¹⁸O?+?24.43 (R²?=?0.98). Pre-event spring discharge showed variation in δ¹⁸O (range ?6.29 to ?7.17?‰; average ?6.58?±?0.19?‰) and δ²H values (range ?28.8 to ?32.7?‰; average: ?30.5?±?1.0?‰). In contrast, δ¹⁸O and δ²H rapidly changed to more negative values during rainfall and snowmelt events and persisted for several days before returning to background values. Spring water temperature, spring discharge, and turbidity followed the trend in isotopic composition during and after the precipitation events. The rapid change in the isotopic composition, spring discharge, water temperature, and turbidity in response to recharge events is related to fast water travel times and low storage capacity in the conduit system of the karst aquifer. Based on the changes in the isotopic composition of spring water after the precipitation events, the water travel time in the aquifer is in the order of 5–11 days.     

The use of stable isotopes to evaluate water mixing and water use by flood plain trees along the Garonne valley

Before the confluence of the Tarn, the Garonne valley was the driest area in the entire south-west of France, due to the relatively low rainfall and low summer discharge of the Garonne River and its tributaries. The natural abundance of the stable isotope of oxygen (¹⁸O) and ionic charge of surface and ground water were used to estimate the water source for the Garonne River and phreatic subsurface water. We also measured these constituents in the sap of trees at several flood plain sites to better understand the source of water used by these trees. ¹⁸O signatures and conductivity in the Garonne River indicated that the predominance of water was from high altitude surface runoff from the Pyrenees Mountains. Tributary inputs had little effect on isotopic identity, but had a small effect on the conductivity. The isotopic signature and ionic conductivity of river water (δ¹⁸O: ?9.1‰ to ?9.0‰, conductivity: 217–410?µS/cm) was distinctly different from groundwater (δ¹⁸O: ?7.1‰ to ?6.6‰, conductivity: 600–900?µS/cm). Isotopic signatures from the sap of trees on the flood plain showed that the water source was shallow subsurface water (<30?cm), whereas trees further from the river relied on deeper ground water (>1?m). Trees at both locations maintained sap with ionic charges much greater (2.3–3.7×) than that of source water. The combined use of ¹⁸O signatures and ionic conductivity appears to be a potent tool to determine water sources on geographic scales, and source and use patterns by trees at the local forest scale. These analyses also show promise for better understanding of the effects of anthropogenic land-use and water-use changes on flood plain forest dynamics.     

Stable isotopic and geochemical variability within shallow groundwater beneath a hardwood hammock and surface water in an adjoining slough (Everglades National Park,Florida, USA)

Data from a 10-month monitoring study during 2007 in the Everglades ecosystem provide insight into the variation of δ¹⁸O, δD, and ion chemistry in surface water and shallow groundwater. Surface waters are sensitive to dilution from rainfall and input from external sources. Shallow groundwater, on the other hand, remains geochemically stable during the year. Surface water input from canals derived from draining agricultural areas to the north and east of the Everglades is evident in the ion data. δ¹⁸O and δD values in shallow groundwater remain near the mean of?2.4 and?12 ‰, respectively. ¹⁸O and D values are enriched in surface water compared with shallow groundwater and fluctuate in sync with those measured in rainfall. The local meteoric water line (LMWL) for precipitation is in close agreement with the global meteoric water line; however, the local evaporation line (LEL) for surface water and shallow groundwater is δ D=5.6 δ¹⁸O+1.5, a sign that these waters have experienced evaporation. The intercept of the LMWL and LEL indicates that the primary recharge to the Everglades is tropical cyclones or fronts. δ deuterium to δ¹⁸O excess (D_ex values) generally reveal two moisture sources for precipitation, a maritime source during the fall and winter (D _ex>10 ‰) and a continental-influenced source (D _ex<10 ‰) in the spring and summer.     

Tree species of the central amazon and soil moisture alter stable isotope composition of nitrogen and oxygen in nitrous oxide evolved from soil

The use of stable isotopes of N and O in N₂O has been proposed as a way to better constrain the global budget of atmospheric N₂O and to better understand the relative contributions of the main microbial processes (nitrification and denitrification) responsible for N₂O formation in soil. This study compared the isotopic composition of N₂O emitted from soils under different tree species in the Brazilian Amazon. We also compared the effect of tree species with that of soil moisture, as we expected the latter to be the main factor regulating the proportion of nitrifier- and denitrifier-derived N₂O and, consequently, isotopic signatures of N₂O. Tree species significantly affected δ ¹⁵N in nitrous oxide. However, there was no evidence that the observed variation in δ ¹⁵N in N₂O was determined by varying proportions of nitrifier- vs. denitrifier-derived N₂O. We submit that the large variation in δ ¹⁵N-N₂O is the result of competition between denitrifying and immobilizing microorganisms for NO 3 m . In addition to altering δ ¹⁵N-N₂O, tree species affected net rates of N₂O emission from soil in laboratory incubations. These results suggest that tree species contribute to the large isotopic variation in N₂O observed in a range tropical forest soils. We found that soil water affects both ¹⁵N and ¹⁸O in N₂O, with wetter soils leading to more depleted N₂O in both ¹⁵N and ¹⁸O. This is likely caused by a shift in biological processes for ¹⁵N and possible direct exchange of ¹⁸O between H₂O and N₂O.     

Bestimmung der 15N Häufigkeit bei nichtstatistischer 15N-verteilung in N2 sowie bei N2O in Bodenluftproben mittels GC-R-IRMS-Kopplung in einem Probenlauf

Abstract

An analysis technique based on GC-R-IRMS coupling (Gas-Chromatography-Reduction-Isotope Ratio Mass Spectrometry) is demonstrated. The ¹⁵N abundance of N² and N²O in atmospheric air or soil atmosphere from nitrification or denitrification processes with nonrandom distribution is determined in one run. The 12 ml sample is separated from CO² and transported by a helium gas stream through a cooling trap. The N²O is trapped in the cooling trap while the N² passes through it and enters the GC. After GC separation and O² removal in a reduction column, part of the N² enters an isotope mass spectrometer to determine the masses m/z 28,29 and 30. The interferences on mass 30 by the formation of NO in the ion source of the mass spectrometer are eliminated by a calibration and a correction procedure. Upon removing the cooling trap, the N²O is injected into the GC, where it is separated and then quantitatively reduced to N² in a reduction column. The measurement of one sample takes 16 minutes. The detection limit of the ³⁰R_t in alteration N₂ is Δ³⁰R_t = 5 · 10^?7. The detection limit of the N₂O is 3.6 nl.     

Release of nitrous oxide and dinitrogen from a transition bog under drained and rewetted conditions due to denitrification: results from a [15N]nitrate–bromide double-tracer study

Denitrification is well known being the most important nitrate-consuming process in water-logged peat soils, whereby the intermediate compound nitrous oxide (N₂O) and the end product dinitrogen (N₂) are ultimately released. The present study was aimed at evaluating the release of these gases (due to denitrification) from a nutrient-poor transition bog ecosystem under drained and three differently rewetted conditions at the field scale using a ¹⁵N-tracer approach ([¹⁵N]nitrate application, 30?kg N ha^?1) and a common closed-chamber technique. The drained site is characterized by a constant water table (WT) of –30?cm (here referred to as D30), while rewetted sites represent a constant WT of –15?cm, a constant WT of 0?cm (i.e. waterlogged), and an initial WT of 0?cm (which decreased slightly during the experiment), respectively, (here referred to as R15, R0, and R0_d, respectively). The highest N₂O emissions were observed at D30 (291?µg N₂O–N m^?2 h^?1) as well as at R0_d (665?µg N₂O–N m^?2 h^?1). At the rewetted peat sites with a constant WT (i.e. R15 and R0), considerably lower N₂O emissions were observed (maximal 37?µg N₂O–N m^?2 h^?1). Concerning N₂ only at the initially water-logged peat site R0_d considerable release rates (up to 3110?µg N₂–N m^?2 h^?1) were observed, while under drained conditions (D30) no N₂ emission and under rewetted conditions with a constant WT (R15 and R0) significantly lower N₂ release rates (maximal 668?µg N₂–N m^–2 h^?1) could be detected. In addition, it has been found that natural WT fluctuations at rewetted peat sites, in particular a rapid drop down of the WT, can induce high emission rates for both N₂O and N₂.     

Sources and circulation of water and arsenic in the Giant Mine,Yellowknife, NWT,Canada

Recovery of gold from arsenopyrite-hosted ore in the Giant Mine camp, Yellowknife, NWT, Canada, has left a legacy of arsenic contamination that poses challenges for mine closure planning. Seepage from underground chambers storing some 237,000 tonnes of arsenic trioxide dust, has As concentrations exceeding 4000 ppm. Other potential sources and sinks of As also exist. Sources and movement of water and arsenic are traced using the isotopes of water and sulphate. Mine waters (16 ppm As; As^V/As^III ≈ 150) are a mixture of two principal water sources – locally recharged, low As groundwaters (0.5 ppm As) and Great Slave Lake (GSL; 0.004 ppm As) water, formerly used in ore processing and discharged to the northwest tailings impoundment (NWTP). Mass balance with δ¹⁸O shows that recirculation of NWTP water to the underground through faults and unsealed drillholes contributes about 60% of the mine water. ;[emsp]>Sulphate serves to trace direct infiltration to the As₂O₃ chambers. Sulphate in local, low As groundwaters (0.3–0.6 ppm As; δ³⁴S_SO4  ～ 4 ‰ and δ¹⁸O_SO4  ～ ? 10 ‰) originates from low-temperature aqueous oxidation of sulphide-rich waste rock. The high As waters gain a component of ¹⁸O-enriched sulphate derived from roaster gases (δ¹⁸O_SO4  = + 3.5 ‰), consistent with their arsenic source from the As₂O₃ chambers. High arsenic in NWTP water (～ 8 ppm As; δ¹⁸O_SO4  = ? 2 ‰) derived from mine water, is attenuated to close to 1 ppm during infiltration back to the underground, probably by oxidation and sorption by ferrihydrite.     

Stable isotopes in river waters in the Tajik Pamirs: regional and temporal characteristics

The Gunt River catchment in the Central Pamirs is a representative of the headwater catchments of the Aral Sea Basin. It covers 14,000 km², spanning altitudes between 2000 and 6700 m a.s.l. In a monitoring network, water samples were taken at 30 sampling points every month and analysed for the stable water isotopes (¹⁸O and ²H). Our first results show δ²H values in the range from?131.2 to?94.9 ‰ and δ¹⁸O values from?18.0 to?14.0 ‰. The stable isotope patterns in the catchment seem to follow a systematic way, dominated by an altitude effect with a mean Δ δ²H=?3.6 ‰/100 m. The observed seasonal variations can be explained by geographical aspects such as the influence of different wind systems as well as melting processes.     

USGS48 Puerto Rico precipitation – a new isotopic reference material for δ2H and δ18O measurements of water

A new secondary isotopic reference material has been prepared from Puerto Rico precipitation, which was filtered, homogenised, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material, designated as USGS48, is intended to be one of two isotopic reference waters for daily normalisation of stable hydrogen (δ²H) and stable oxygen (δ¹⁸O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The δ²H and δ¹⁸O values of this reference water are?2.0±0.4 and?2.224±0.012 ‰, respectively, relative to Vienna Standard Mean Ocean Water on scales normalised such that the δ²H and δ¹⁸O values of Standard Light Antarctic Precipitation reference water are?428 and?55.5 ‰, respectively. Each uncertainty is an estimated expanded uncertainty (U=2u_c) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. This isotopic reference water is available by the case of 144 glass ampoules containing 5 mL of water in each ampoule.