A method for the analysis of the δ18O of inorganic phosphate extracted from soils with HCl

The oxygen isotope composition of phosphate (δ¹⁸O‐PO₄) has successfully been used to study the biological cycling of phosphorus (P) in seawater and marine sediments. However, only a few studies have used this approach in soils. In order to analyse δ¹⁸O‐PO₄, phosphate must be extracted from the soil, purified and converted to silver phosphate (Ag₃PO₄). The published extraction methods, successfully applied to marine waters and sediments, lead to the precipitation of impure Ag₃PO₄when used with soils or organic‐rich samples. Here we present an improved purification protocol, designed for soils and other organic‐rich samples. After extraction with HCl, phosphate is purified with multiple mineral precipitations that do not require extreme pH adjustments of the solutions. We show that contaminant‐free Ag₃PO₄ can be produced from fertilizers and various soils with different chemical and physical characteristics. Our first isotopic results confirm that differences in P status and availability in soils are expressed in the δ¹⁸O‐PO₄ signal, indicating the potential of this isotopic tracer to understand P dynamics in soil systems.     

Short‐term sequestration of slurry‐derived carbon and nitrogen in temperate grassland soil as assessed by 13C and 15N natural abundance measurements

Land application of animal wastes from intensive grassland farming has caused growing environmental problems during the last decade. This study aimed to elucidate the short‐term sequestration of slurry‐derived C and N in a temperate grassland soil (Southwest England) using natural abundance ¹³C and ¹⁵N stable isotope techniques. Slurry was collected from cows fed either on perennial ryegrass (C3) or maize (C4) silages. 50 m³ ha^—1 of each of the obtained C3 or C4 slurries (δ¹³C = —30.7 and —21.3‰, δ¹⁵N = +12.2 and + 13.8 ‰, respectively) were applied to a C₃ soil with δ¹³C and δ¹⁵N values of —30.0 ± 0.2‰ and + 4.9 ± 0.3‰, respectively. Triplicate soil samples were taken from 0—2, 2—7.5, and 7.5—15 cm soil depth 90 and 10 days before, at 2 and 12 h, as well as at 1, 2, 4, 7, and 14 days after slurry application and analyzed for total C, N, δ¹³C, and δ¹⁵N. No significant differences in soil C and N content were observed following slurry application using conventional C and N analysis techniques. However, natural abundance ¹³C and ¹⁵N isotope analysis allowed for a sensitive temporal quantification of the slurry‐derived C and N sequestration in the grassland soil. Our results showed that within 12 hours more than one‐third of the applied slurry C was found in the uppermost soil layer (0—2 cm), decreasing to 18% after 2 days, but subsequently increasing to 36% after 2 weeks. The tentative estimate of slurry‐derived N in the soil suggested a decrease from 50% 2 hours after slurry application to only 26% after 2 weeks, assuming that the increase in δ¹⁵N of the slurry plots compared to the control is proportional to the amount of slurry‐incorporated N. We conclude that the natural abundance tracer technique can provide a rapid new clue to the fate of slurry in agricultural C and N budgets, which is important for environmental impacts, farm waste management, and climate change studies.     

Tracing sources of soil nitrate using the dual isotopic composition of nitrate in 2 M KCl-extracts

Soils comprise a critical interface between the atmosphere, lithosphere, hydrosphere and biosphere, and play a major role in the cycling of nitrogen (N), an element crucial to plant growth. Isotope techniques constitute a powerful tool to study the origin and fate of N compounds (e.g. NO₃⁻) within the environment including soils. The objective of our study was to test the usefulness of the isotope composition of soil NO₃⁻ extracted with 2 M KCl (soil NO₃) as a tool to investigate the origin and fate of NO₃⁻ in the environment. Specifically issues related to repeat extractions, crop type, length of fertilization, and soil depth were addressed. Soils from four contrasting agricultural management regimes were sampled. Within the relatively confined study area (4 ha), the isotopic compositions of soil NO₃ differed markedly due to management treatments (up to 6 and 17‰ for δ¹⁵N and δ¹⁸O, respectively), but were repeatable among replicate plots (±1‰). Differences in both δ¹⁵N and δ¹⁸O values were observed between legume and non-legume treatments, as well as fertilized versus non-fertilized treatments, which were larger than the variability observed between replicate plots. Differences in the isotopic composition of extractable soil nitrate were not limited to the surface layer, but also occurred within deeper soil layers. This study indicates that the analysis of the natural abundance stable isotope composition of soil NO₃ may provide a promising additional tool for tracing the origin and fate of NO₃⁻ in the soil zone.     

Sampling water from alfalfa (Medicago sativa) for analysis of stable isotopes of water

Abstract

The isotopic composition of water extracted from various parts of alfalfa (Medicago saliva) plants was compared with that transpired by the plants to validate water extraction procedures, and to define the degree of alteration of the isotopic composition of water that occurred in different plant parts. The mean δ²H and δ¹⁸O values of water extracted from the upper tap root and lower crown regions were < 1‰ and 0.3‰ different from that of water transpired, respectively, with an analytical precision similar to that found in previous studies on soils and trees. Water from other plant parts closer to the leaves was enriched in ²H (up to 12.6 in upper stems) and ¹⁸O (4.2‰) with respect to that transpired. The enrichment was associated with a greater variability in δ²H values between replicate plants. δ²H‐δ¹⁸O data indicated that the isotopic enrichment was due to evaporation during transpiration. The study showed that azeotropic distillation is an accurate means of extracting water from alfalfa, although care is required when obtaining plant samples for comparison with water from the root‐zone.     

Isotopomer analysis of nitrous oxide accumulated in soil cultivated with tea (Camellia sinensis) in Shizuoka,central Japan

Nitrous oxide (N₂O) is a greenhouse gas that is destroying the stratospheric ozone to an increasing degree. Because of nitrogenous fertilizer application, agricultural soil is an important contributor of global N₂O. In Japan, tea fields are amended with the highest level of N fertilizers among agricultural soils, causing soil acidification and large N₂O flux. In soil, microbes play key roles in producing and consuming N₂O. A previous study investigated net N₂O production in tea fields using N₂O flux measurement and soil incubation, which are indirect methods to analyze relevant processes of N₂O production and consumption in soil. In the present study, to analyze N₂O concentrations and isotopomer ratios (bulk nitrogen and oxygen isotope ratios, δ¹⁵N^bulk and δ¹⁸O, and intramolecular ¹⁵N site preference, SP) and to reveal most probable microbial production processes and consumption (N₂O reduction to N₂) process of N₂O, soil gas was collected from a tea field (pH 3.1–4.5) at 10–50 cm depths using a silicone tube. The combination of fertilization, precipitation, and temperature rise produced significantly high N₂O concentrations. During the period of high N₂O concentration (above 5.7 ppmv), SP, the difference in ¹⁵N/¹⁴N ratio between central (α) and terminal (β) nitrogen position in the linear N₂O molecule (^βN^αNO) showed low values of 1.4‰–9.8‰, suggesting that the contribution of bacterial denitrification (nitrifier-denitrification and bacterial denitrifier-denitrification) was greater than that of bacterial nitrification or fungal denitrification. High SP values of 15.0‰–20.1‰ obtained at 10, 35, and 50 cm depths on 31 May 2011 (after one of fertilizations) during which soil temperatures were 15.8 °C–17.9 °C and water-filled pore space (WFPS) was 0.73–0.89 suggest that fungal denitrification and bacterial nitrification contributed to N₂O production to a degree equivalent to that of bacterial denitrification.     

有机物对红外光谱技术测定植物叶片和茎秆水δ18O和δD的影响

植物叶片、茎秆和土壤水δ18O和δD是研究土壤植被大气系统生态水文循环过程的重要示踪剂。与传统的稳定同位素质谱(IRMS)技术相比,稳定同位素红外光谱(IRIS)技术具有测量速度快、运行成本低等优势,将促进稳定同位素生态学的发展。但是利用低温真空蒸馏抽提技术获得的植物叶片和茎秆水中含有甲醇和乙醇类有机污染物,造成δ18O和δD的IRIS测量值偏离IRMS测量值(2.64±0.43)‰和(3.6±0.8)‰,超过了仪器精度。本研究利用纯水混入不同浓度的色谱纯甲醇或乙醇,结合Los Gatos公司的光谱分析软件确定甲醇(NB)和乙醇(BB)类物质污染程度的光谱度量值,建立了δ18O和δD的光谱污染校正方法。研究表明,同一台分析仪建立的校正曲线无明显的时间漂移;不同分析仪建立的校正曲线存在显著差异;IRIS校正值与IRMS测量值的交叉验证表明,IRIS测定冬小麦和夏玉米叶片和茎秆水的δ18O和δD可以被准确地校正,与IRMS的差值分别为(0.11±0.12)‰和(0.7±0.4)‰。     

The δ18O signatures of HCl‐extractable soil phosphates: methodological challenges and evidence of the cycling of biological P in arable soil

Soil phosphates exchange oxygen atoms rapidly with soil water once recycled by intracellular enzymes, thereby approaching an equilibrium δ¹⁸O_P signature that depends on ambient temperature and the δ¹⁸O_W signature of soil water. We hypothesized that in the topsoil, phosphates reach this equilibrium δ¹⁸O_P signature even if amended by different fertilizers. In the subsoil, however, there might be phosphates with a smaller δ¹⁸O_P value than that represented by the isotopic equilibrium value, a condition that could exist in the case of limited biological P cycling only. We tested these hypotheses for the HCl‐extractable P pool of the Hedley fractionation scheme of arable soil in Germany, which integrates over extended time‐scales of the soil P cycle. We sampled several types of fertilizer, the surface soil that received these fertilizer types and composites from a Haplic Luvisol depth profile under long‐term agricultural practice. Organic fertilizers had significantly smaller δ¹⁸O_P values than mineral fertilizers. Intriguingly, the fields fertilized organically also tended to have smaller δ¹⁸O_P signatures than other types of surface soil, which calls into question full isotopic equilibrium at all sites. At depths below 50 cm, the soil δ¹⁸O_P values were even depleted relative to the values calculated for isotopic equilibrium. This implies that HCl‐extractable phosphates in different soil horizons are of different origins. In addition, it supports the assumption that biological cycling of P by intracellular microbial enzymes might have been relatively inefficient in the deeper subsoil. At depths of 50–80 cm, there was a transition zone of declining δ¹⁸O_P values, which might be regarded as the first evidence that the degree of biological P cycling changed at this depth interval.     

Seasonal Changes of Shoot Nitrogen Concentrations and 15N/14N Ratios in Common Reed in a Constructed Wetland

Abstract

Nitrogen (N) concentrations and stable N isotope abundances (δ¹⁵N) of common reed (Phragmites australis) planted in a constructed wetland were measured periodically between July 2001 and May 2002 to examine their seasonal variations in relation to N uptake and N translocation within common reed. Nitrogen concentrations in P. australis shoots were higher in the growing stage (7.5 to 24.8 g N kg^?1) than in the senescence stage (4.2 to 6.8 g N kg^?1), indicating N translocation from shoots to rhizomes. Meanwhile, the corresponding δ¹⁵N values were higher in the senescence stage (+12.2 to +22.4‰) than in the growing stage (+5.1 to +11.3‰). Coupled with the negative correlation (R²=0.24, P<0.05, n=18) between N concentrations and δ¹⁵N values of shoots in the senescence stage, our results suggested that shoot N became enriched in ¹⁵N due to N isotopic fractionation (with an isotopic fractionation factor, α_s/p, of 1.012) during N translocation to rhizomes. However, the positive correlation between N concentrations and δ¹⁵N values in the growing stage (R²=0.19, P<0.001, n=54) suggested that P. australis relies on N re‐translocated from rhizome in the early growing stage and on mineral N in the sediment during the active growing stage. Therefore, seasonal δ¹⁵N variations provide N‐isotopic evidence of N translocation within and N uptake from external N sources by common reed.     

Short-term changes in amino sugar-specific δ13C values after application of C4 and C3 sucrose

Amino sugars are useful indicators for the accumulation of microbial residues. A 14-day incubation experiment with C4 and C3 sucrose additions was carried out to investigate the relationships between amino sugar-specific shifts in δ¹³C values and those of CO₂ production, microbial biomass C, K₂SO₄ extractable C and soil organic C (SOC). High performance anion exchange chromatography (HPAEC-IRMS) was able to measure amino-sugar specific δ¹³C values for muramic acid (MurN), galactosamine (GalN), and glucosamine (GlcN) in the range of natural abundance. At day 7, the initial application of C4 sucrose significantly increased the δ¹³C value of MurN by 1.0‰ in comparison with the non-amended control treatment, whereas that of GalN and GlcN remained unchanged. This significant increase had disappeared by day 14. This means that the HPAEC-IRMS method is not useful for short-term incubation experiments in the natural abundance range, as the pool size, especially of GalN and GlcN, was too large for a significant response in δ¹³C values. The δ¹³C values significantly decreased in the order MurN (−23.2‰) > GalN (−25.7‰) > GlcN (−26.5‰) in the control treatment. Similar δ¹³C values were measured in GlcN, microbial biomass C, and SOC. MurN exhibited δ¹³C values similar to the K₂SO₄ extractable fraction. These results may be caused by differences in the access of bacteria and fungi to different SOC fractions or differences in metabolic fractionation in bacteria and fungi. C3 sucrose application without further nutrient supply seven days after C4 sucrose application together with N and P led to strong mineralization of freshly formed microbial residues.     

Perspectives from the Fritz‐Scheffer Awardee 2019. Oxygen isotopes in phosphate—The key to phosphorus tracing?

Phosphorus (P) tracing in natural environments is challenging, lacking stable P isotopes Oxygen isotope ratios in phosphate (δ¹⁸O_P) represent a novel tool for tracing the biological cycling of P from the global scale down to hotspots at the micro‐scale and within particular soil compartments such as aggregates or pores. Despite the small number of studies available so far, existing data indicate that δ¹⁸O_P values point to where, at what extent and how efficiently P is recycled in soils.     

δ34S variations in vegetation and soil exposed to intense biogenic sulphide emissions near Paige mountain,N.W.T., Canada

Sulphur isotope abundances demonstrate that natural emissions of biogenic H₂S and its oxidation products from springs near Paige Mountain, N.W.T., Canada, can be incorporated into surrounding soil and vegetation. δ³⁴S values as low as ? 33‰ for soil and vegetation are the result of dominant uptake of biogenic atmospheric compounds. In contrast, vegetation on a gypsum outcrop remote from the springs, has δ³⁴S values as high as + 26‰ indicating nearly exclusive derivation of S from the soil. Near the springs, soil with vegetative cover is less depleted in ³⁴S than soil lacking cover. Lower needles on a Black Spruce were found to be less depleted in ³⁴S than the upper needles. These observations suggest that upper foliage exerts a canopy effect on lower foliage and in turn, interception by vegetation reduces the flux of atmospheric S compounds to the soil. Clearly, natural emissions of S compounds can interfere in studies of long range transport of industrial emissions; S isotope analyses might identify such interferences and reduce the chance of misinterpretation.     

Natural abundance of 18O of sugar biomarkers in topsoils along a climate transect over the Central Scandinavian Mountains,Norway

Precipitation and topsoil samples from a climate transect over the Scandinavian Mountains, Norway, were analyzed for bulk and compound‐specific δ¹⁸O values. The natural abundance of ¹⁸O in the plant‐derived hemicellulose biomarkers arabinose and xylose correlates positively with δ¹⁸O of bulk soil, but not with δ¹⁸O of precipitation. This suggests that other factors than δ¹⁸O_prec, such as evaporative ¹⁸O enrichment of leaf water, exert a strong influence on the natural abundance of ¹⁸O in soils.     

Inorganic and organic carbon dynamics in forested soils developed on contrasting geology in Slovenia—a stable isotope approach

Purpose

Soil carbon dynamics were studied at four different forest stands developed on bedrocks with contrasting geology in Slovenia: one plot on magmatic granodiorite bedrock (IG), two plots on carbonate bedrock in the karstic-dinaric area (CC and CD), and one situated on Pleistocene coalluvial terraces (FGS).

Materials and methods

Throughfall (TF) and soil water were collected monthly at each location from June to November during 2005–2007. In soil water, the following parameters were determined: T, pH, total alkalinity, concentrations of Ca²⁺ and Mg²⁺, dissolved organic carbon (DOC), and Cl^? as well as δ¹³C_DIC. On the other hand, in TF, only the Cl^? content was measured. Soil and plant samples were also collected at forest stands, and stable isotope measurements were performed in soil and plant organic carbon and total nitrogen and in carbonate rocks. The obtained data were used to calculate the dissolved inorganic carbon (DIC) and DOC fluxes. Statistic analyses were carried out to compare sites of different lithologies, at different spatial and temporal scales.

Results and discussion

Decomposition of soil organic matter (SOM) controlled by the climate can explain the ¹³C and ¹⁵?N enrichment in SOM at CC, CD, and FGS, while the soil microbial biomass makes an important contribution to the SOM at IG. The loss of DOC at a soil depth of 5 cm was estimated at 1 mol m^?2 year^?1 and shows no significant differences among the study sites. The DOC fluxes were mainly controlled by physical factors, most notably sorption dynamics, and microbial–DOC relationships. The pH and pCO₂ of the soil solution controlled the DIC fluxes according to carbonate equilibrium reactions. An increased exchange between DIC and atmospheric air was observed for samples from non-carbonate subsoils (IG and FGS). In addition, higher δ¹³C_DIC values up to ?19.4?‰ in the shallow soil water were recorded during the summer as a consequence of isotopic fractionation induced by molecular diffusion of soil CO₂. The δ¹³C_DIC values also suggest that half of the DIC derives from soil CO₂ indicating that 2 to 5 mol m^?2 year^?1 of carbon is lost in the form of dissolved inorganic carbon at CC and CD after carbonate dissolution.

Conclusions

Major difference in soil carbon dynamics between the four forest ecosystems is a result of the combined influence of bedrock geology, soil texture, and the sources of SOM. Water flux was a critical parameter in quantifying carbon depletion rates in dissolved organic and inorganic carbon forms.

     

Sulfur isotope dynamics in a high-elevation catchment,West Glacier lake,Wyoming

Stable isotopes of S are used in conjunction with dissolved SO ₄ ^2? concentrations to evaluate the utility ofδ ³⁴S ratios in tracing contributions of bedrock-derived S to SO ₄ ^2? in runoff. Water samples were collected over the annual hydrograph from two tributaries in the West Glacier Lake, Wyoming, catchment. Concentrations of SO ₄ ^2? ranged from 12.6 to 43.0 Μeq L^?1;δ ³⁴S ratios ranged from ?1.8‰ to +4.9‰ Theδ ³⁴S value of atmospherically derived SO ₄ ^2? is about +5.6%c.; four samples of pyrite from the bedrock hadδ ³⁴S ratios that ranged from +0.7 to +4.1‰ Concentrations of SO ₄ ^2? were inversely related toδ ³⁴S and discharge. The data for the tributary with the higher SO ₄ ^2? concentrations were reasonably consistent with mixing between atmospheric S and S from a bedrock source with aδ ³⁴S ratio of about ?4.5‰. The difference from the measured bedrock values presumably indicates that S isotopes in the bedrock pyrite are heterogeneously distributed. The data from the tributary with lower SO ₄ ^2? concentrations did not follow a two-component mixing line. Deviation from a two-component mixing line is most likely caused by preferential elution of SO ₄ ^2? from the snowpack during the early stages of snowmelt, although microbially mediated fractionation of S isotopes in the soil zone also may cause the deviation from the mixing line. Sulfur isotopes are useful in identifying whether or not there is a substantial contribution of bedrock S to runoff, but quantifying that contribution is problematic.     

Impact of Soil Sorption Characteristics and Bedrock Composition on Phosphorus Concentrations in two Bohemian Forest Lakes

Phosphate (PO₄-P) sorption characteristics of soils and bedrock composition were determined in catchments of two mountain lakes, Ple?né Lake (PL) and ?ertovo Lake (CT), situated in the Bohemian Forest (Czech Republic). The aim was to explain higher terrestrial P export to mesotrophic PL compared to oligotrophic CT. Concentrations of Al and Fe oxides were the dominant parameters affecting soil ability to adsorb PO₄-P. Depending on concentrations of Al and Fe oxides, P sorption maxima varied from 9.7 to 70.5 mmol kg^?1 and from 7.4 to 121 mmol kg^?1 in organic and mineral soil horizons, respectively. The catchment weighted mean PO₄-P sorption capacity was 3.4 mol m^?2 and 11.9 mol m^?2 in the PL and CT soils, respectively. The higher PO₄-P sorption capacity in the CT catchment was predominantly associated with higher pools of soil and Fe oxides. The CT bedrock (mica schist) released one order of magnitude less P than the PL bedrock (granite) within a pH range of catchment soils (pH_CaCl2 of 2.5–4.5). The higher ability of PL bedrock to release P and the lower ability of PL soils to adsorb PO₄-P thus contributed to the higher terrestrial P loading of this lake.     

Dual isotope and isotopomer measurements for the understanding of N2O production and consumption during denitrification in an arable soil

The aim of our research was to obtain information on the isotopic fingerprint of nitrous oxide (N₂O) associated with its production and consumption during denitrification. An arable soil was preincubated at high moisture content and subsequently amended with glucose (400 kg C ha^?1) and KNO₃ (80 kg N ha^?1) and kept at 85% water‐filled pore space. Twelve replicate samples of the soil were incubated for 13 days under a helium‐oxygen atmosphere, simultaneously measuring gas fluxes (N₂O, N₂ and CO₂) and isotope signatures (δ¹⁸O‐N₂O, δ¹⁵N^bulk‐N₂O, δ¹⁵N^α, δ¹⁵N^β and ¹⁵N site preference) of emitted N₂O. The maximum N₂O flux (6.9 ± 1.8 kg N ha^?1 day^?1) occurred 3 days after amendment application, followed by the maximum N₂ flux on day 4 (6.6 ± 3.0 kg N ha^?1 day^?1). The δ¹⁵N^bulk was initially ?34.4‰ and increased to +4.5‰ during the periods of maximum N₂ flux, demonstrating fractionation during N₂O reduction, and then decreased. The δ¹⁸O‐N₂O also increased, peaking with the maximum N₂ flux and remaining stable afterwards. The site preference (SP) decreased from the initial +7.5 to ?2.1‰ when the N₂O flux peaked, and then simultaneously increased with the appearance of the N₂ peak to +8.6‰ and remained stable thereafter, even when the O₂ supply was removed. We suggest that this results from a non‐homogenous distribution of NO in the soil, possibly linked to the KNO₃ amendments to the soil, causing the creation of several NO pools, which affected differently the isotopic signature of N₂O and the N₂O and N₂ fluxes during the various stages of the process. The N₂O isotopologue values reflected the temporal patterns observed in N₂O and N₂ fluxes. A concurrent increase in ¹⁵N site preference and δ¹⁸O of N₂O was found to be indicative of N₂O reduction to N₂.     

Sources of Nitrate in Snowmelt Discharge: Evidence From Water Chemistry and Stable Isotopes of Nitrate

To determine whether NO₃ ^? concentration pulses in surface water in early spring snowmelt discharge are due to atmospheric NO₃ ^?, we analyzed stream δ¹⁵N-NO₃ ^? and δ¹⁸O-NO₃ ^? values between February and June of 2001 and 2002 and compared them to those of throughfall, bulk precipitation, snow, and groundwater. Stream total Al, DOC and Si concentrations were used to indicate preferential water flow through the forest floor, mineral soil, and ground water. The study was conducted in a 135-ha subcatchment of the Arbutus Watershed in the Huntington Wildlife Forest in the Adirondack Region of New York State, U.S.A. Stream discharge in 2001 increased from 0.6 before to 32.4 mm day^?1 during snowmelt, and element concentrations increased from 33 to 71 μmol L^?1 for NO₃ ^?, 3 to 9 μmol L^?1 for total Al, and 330 to 570 μmol L^?1 for DOC. Discharge in 2002 was variable, with a maximum of 30 mm day^?1 during snowmelt. The highest NO₃ ^?, Al, and DOC concentrations were 52, 10, and 630 μmol L^?1, respectively, and dissolved Si decreased from 148 μmol L^?1 before to 96 μmol L^?1 during snowmelt. Values of δ¹⁵N and δ¹⁸O of NO₃ ^? in stream water were similar in both years. Stream water, atmospherically-derived solutions, and groundwaters had overlapping δ¹⁵N-NO₃ ^? values. In stream and ground water, δ¹⁸O-NO₃ ^? values ranged from +5.9 to +12.9‰ and were significantly lower than the +58.3 to +78.7‰ values in atmospheric solutions. Values of δ¹⁸O-NO₃ ^? indicating nitrification, increase in Al and DOC, and decrease in dissolved Si concentrations indicating water flow through the soil suggested a dilution of groundwater NO₃ ^? by increasing contributions of forest floor and mineral soil NO₃ ^? during snowmelt.     

Effect of antecedent soil moisture conditions on emissions and isotopologue distribution of N2O during denitrification

The present study determined the influence of initial moisture conditions on the production and consumption of nitrous oxide (N₂O) during denitrification and on the isotopic fingerprint of soil-emitted N₂O. Sieved arable soil was pre-incubated at two different moisture contents: pre-wet at 75% and pre-dry at 20% water-filled pore space. After wetting to 90% water-filled pore space the soils were amended with glucose (400 kg C ha⁻¹) and KNO₃ (80 kg N ha⁻¹) and incubated for 10 days under a He/O₂-atmosphere. Antecedent moisture conditions affected denitrification. N₂ + N₂O fluxes and the N₂O-to-N₂ ratio were higher in soils which were pre-incubated under dry conditions, probably because mobilization of organic C during the pre-treatment enhanced denitrification. Gaseous N fluxes showed similar time patterns of production and reduction of N₂O in both treatments, where N₂O fluxes were initially increasing and maximised 3-4 days after fertilizer application, and N₂ fluxes were delayed by 1-2 days. Time courses of δ¹⁵N^bulk-N₂O and δ¹⁸O-N₂O exhibited in both treatments increasing trends until maximum N₂ fluxes occurred, reflecting isotope fractionation during intense NO₃⁻ reduction. Later this trend slowed down in the pre-dry treatment, while δ¹⁸O-N₂O was constant and δ¹⁵N^bulk-N₂O decreased in the pre-wet treatment. We explain these time patterns by non-homogenous distribution of NO₃⁻ and denitrification activity, resulting from application of NO₃⁻ and glucose to the surface of the soil. We assume that several process zones were thus created, which affected differently the isotopic signature of N₂O and the N₂O and N₂ fluxes during the different stages of the process. We modelled the δ¹⁵N^bulk-N₂O using process rates and associated fractionation factors for the pre-treated soils, which confirmed our hypothesis. The site preference (SP) initially decreased while N₂O reduction was absent, which we could not explain by the N-flux pattern. During the subsequent increase in N₂ flux, SP and δ¹⁸O-N₂O increased concurrently, confirming that this isotope pattern is indicative for N₂O reduction to N₂. The possible effect of the antecedent moisture conditions of the soil on N₂O emissions was shown to be important.     

sulphur isotope composition of stream water,moss and humus from eight arctic catchments in the Kola Peninsula region (NW Russia,N Finland,NE Norway)

In summer 1994, stream water, moss and humus samples were collected for sulphur isotopic analysis from eight catchments located in the western Kola Peninsula region, where several industrial centres emit high loads of SO₂ and other elements to the atmosphere. Three potential sources of sulphur and their isotopic signatures were identified: (1) marine (δ ³⁴S+20 to +21‰ CDT), (2) anthropogenic emissions (<+10‰), and (3) geogenic (variableδ ³⁴S, mostly <+10‰). Averaged per catchment, the sulphur isotopic composition varies between +6.0 and +16.3‰ for stream water sulphate, +6.0 and +8.4‰ for moss sulphur, and +5.2 and +12.2‰ for humus sulphur. Theδ ³⁴S composition of stream water from the more remote catchments is quite variable, reflecting several natural (geogenic) sources, but it becomes restricted to the range +8 to +10‰ near the pollution sources. A plot ofδ ³⁴S vs. 1:SO₄ in stream water suggests that sulphate originating from the smelters has aδ ³⁴S value ≈+9.5‰, and is a dominant source. Sulphur isotope values for moss and humus are consistent with the deduced composition for the emitted sulphur, though for humus a component of geogenic sulphur incorporated via vegetation uptake may play a role. Further isotopic characterisation of atmospheric emissions, together with environmental samples, is needed to better understand sulphur sources and sinks in the area.     

Oxygen isotope ratios of plant available phosphate in lowland tropical forest soils

Phosphorus (P) cycles rapidly in lowland tropical forest soils, but the process have been proven difficult to quantify. Recently it was demonstrated that valuable data on soil P transformations can be derived from the natural abundance of stable oxygen isotopes in phosphate (δ¹⁸O_P). Here, we measured the δ¹⁸O_P of soils that had received long-term nutrient additions (P, nitrogen, and potassium) or litter manipulations in lowland tropical forest in Panama and performed controlled incubations of fresh soils amended with a single pulse of P. To detect whether δ¹⁸O_P values measured in the incubations apply also for soils in the field, we examined the δ¹⁸O_P values after rewetting dry soils. In the incubations, resin-P δ¹⁸O_P values converged to ∼3.5‰ above the expected isotopic equilibrium with soil water. This contrasts with extra-tropical soils in which the δ¹⁸O_P of resin-P matches the expected equilibrium with soil water. Identical above-equilibrium resin-P δ¹⁸O_P values were also found in field soils that did not receive P additions or extra litter. We suggest that the 3.5‰ above-equilibrium δ¹⁸O_P values reflect a steady state between microbial uptake of phosphate (which enriches the remaining phosphate with the heavier isotopologues) and the release of isotopically equilibrated cell internal phosphate back to the soil. We also found that soil nutrient status affected the microbial turnover rate because in soils that had received chronic P addition, the original δ¹⁸O_P signature of the fertilizer was preserved for at least eight weeks, indicating that the off-equilibrium δ¹⁸O_P values produced during microbial phosphate turnover was not imprinted in these soils. Overall, our results demonstrate that ongoing microbial turnover of phosphate mediates its biological availability in lowland tropical soils.