Sulfate Reduction in a Forested Catchment as Indicated by δ34S Values of Sulfate in Soil Solutions and Runoff

Abstract

In a forested catchment in the Fichtelgebirge mountains (NE-Bavaria, Germany) the long term SO₄ ^2- budget (average 1988–1994) indicated that about 40% of the input with throughfall (16.8 kg SO₄ ^2- S·ha^?1·yr^?1) was retained in the catchment. In order to identify processes acting as potential SO₄ ^2- sinks, δ³⁴S values of SO₄ ^2- in soil solutions and runoff were measured between May and November 1994. δ³⁴S values of the runoff and the fen were higher (5.8‰) than the δ³⁴S values of the soil solution of the oxic soils in the terrestrial area (3.9‰). Because there is no lithogenic S source within the catchment, it can be assumed that SO₄ ^2- deposition is the only S source in the catchment. Thus the results were interpreted as a result of SO₄ ^2- reduction within the catchment, because the uptake of ³²S is favoured during the dissimilatory SO₄ ^2- reduction and ³⁴S is consequently enriched in the soil solution. To estimate the amount of SO₄ ^2- reduced isotopic fractionation factors between ? 9‰ and ?46‰ were considered, resulting in SO₄ ^2- reduction rates of 1.8–9.3 kg SO₄ ²-S·ha^?1yr^?1. It was concluded that besides dissimilatory SO₄ ^2- reduction another sink exists in the catchment (e.g. SO₄ ^2- sorption in deep soil layers).     

The Effect of Diet Quality on δ13C and δ15N in the Tissues of Locusts,Locusta migratoria L

Abstract

Locust nymphs were raised from hatching to adult locusts on either seedling wheat (C₃) or maize (C₄), to determine whether relative enrichments/depletions of ¹⁵N and ¹³C within body tissues are influenced by diet. The maize contained less hexose sugars and protein per gram than wheat.

The isotopic spacing between the food and the whole insect was found to differ between the two diets. The lower quality maize diet showed an overall +5.1‰ enrichment in δ¹⁵N compared to + 2.8‰ for wheat, possibly due to increased fractionation due to protein recycling.

The maize diet resulted in increased depletion in lipid and trehalose and depletion in chitin relative to diet. The results for both δ¹⁵N and δ¹³C suggest that substrate recycling was occurring on the low quality maize diet. Therefore diet quality determines the enrichment/depletion in δ¹⁵N and δ¹³C within organisms.     

A Sensitive Method for the Fast and Simultaneous Determination of δ15N- and δ18O-Values in Nitrate

A new method for on-line measurements of the isotopic abundances of N and O in nitrate using a Pyrolysis-GC-IRMS system is presented. The salt is heated to 1200°C together with graphite powder, the reaction products are separated by a GC column and allowed into an IRMS. The sample size could be reduced to 200 nmoles element for one measurement, which can be performed within 10 minutes with an accuracy of better than 1‰.     

Sulfate Reduction in a Forested Catchment as Indicated by δ(34)S Values of Sulfate in Soil Solutions and Runoff

Abstract In a forested catchment in the Fichtelgebirge mountains (NE-Bavaria, Germany) the long term SO(4) (2-) budget (average 1988-1994) indicated that about 40% of the input with throughfall (16.8 kg SO(4) (2-) S·ha(-1)·yr(-1)) was retained in the catchment. In order to identify processes acting as potential SO(4) (2-) sinks, δ(34)S values of SO(4) (2-) in soil solutions and runoff were measured between May and November 1994. δ(34)S values of the runoff and the fen were higher (5.8‰) than the δ(34)S values of the soil solution of the oxic soils in the terrestrial area (3.9‰). Because there is no lithogenic S source within the catchment, it can be assumed that SO(4) (2-) deposition is the only S source in the catchment. Thus the results were interpreted as a result of SO(4) (2-) reduction within the catchment, because the uptake of (32)S is favoured during the dissimilatory SO(4) (2-) reduction and (34)S is consequently enriched in the soil solution. To estimate the amount of SO(4) (2-) reduced isotopic fractionation factors between - 9‰ and -46‰ were considered, resulting in SO(4) (2-) reduction rates of 1.8-9.3 kg SO(4) (2)-S·ha(-1)yr(-1). It was concluded that besides dissimilatory SO(4) (2-) reduction another sink exists in the catchment (e.g. SO(4) (2-) sorption in deep soil layers).     

Canopy Gradients in δ18O of Organic Matter as Ecophysiological Tool

Abstract

We determined vertical oxygen isotope gradients of leaf organic matter for a grassland in Switzerland and a mountain beech forest (Fagus sylvatica) in Northern Italy. A distinctly positive ¹⁸O/¹⁶O gradient with height above ground was found for the grassland (7.9‰m^?1, p < 0.001), whereas the gradient was negative for the forest (–0.077‰m^?1, p < 0.001). The results are consistent with microclimatic measurements, although large isotope variations between the species have to be taken into account for the grassland. A conceptual scheme is shown which relates the isotope enrichment to the canopy density, considering the effects of transpiration and canopy structure. We conclude that the analysis of the within canopy variation in δ¹⁸O of organic matter can be used to provide long-term estimates of leaf water isotope composition, thus improving existing isotope methods to determine the gas-exchange between vegetation and atmosphere.     

The Effect of Diet Quality on δ(13)C and δ(15)N in the Tissues of Locusts, Locusta migratoria L

Abstract Locust nymphs were raised from hatching to adult locusts on either seedling wheat (C(3)) or maize (C(4)), to determine whether relative enrichments/depletions of (15)N and (13)C within body tissues are influenced by diet. The maize contained less hexose sugars and protein per gram than wheat. The isotopic spacing between the food and the whole insect was found to differ between the two diets. The lower quality maize diet showed an overall +5.1‰ enrichment in δ(15)N compared to + 2.8‰ for wheat, possibly due to increased fractionation due to protein recycling. The maize diet resulted in increased depletion in lipid and trehalose and depletion in chitin relative to diet. The results for both δ(15)N and δ(13)C suggest that substrate recycling was occurring on the low quality maize diet. Therefore diet quality determines the enrichment/depletion in δ(15)N and δ(13)C within organisms.     

The effect of different fish feed compositions on δ13C and δ15N signatures of sea bass and its potential value for tracking mariculture-derived nutrients

Increasing demand for fish and seafood calls for an expansion of aquaculture production. At the same time, the status of the marine environment must not be jeopardised. Stable isotopes are potential markers for tracking feed-based nutrient flows from aquaculture into marine biota. Here, we demonstrate how four experimental diets (main protein components: fishmeal, soya protein concentrate, wheat gluten, and Jatropha kernel meal) and a commercial diet induce characteristic δ¹³C and δ¹⁵N signals in sea bass (Dicentrarchus labrax) during nine weeks of laboratory feeding under replicate conditions. The plant-protein-based diets containing wheat gluten and soya, and the commercial feed consistently induced the largest isotopic differentiation of the fish, both from the feed source and from the pre-experimental condition. The large difference of the fish on plant-protein-based diets compared to the range of natural isotopic variation in the macrozoobenthos of the North Sea lends support to the idea that plant-based feeds are suitable for tracing mariculture-derived organic matter under practical conditions. The commercial feed had a similar effect as the experimental feeds and would be a cost-effective option for an offshore aquaculture experiment.     

Food Web Implications of δ13C and δ15N Variability over 370 km of the Regulated Colorado River USA

Abstract

Dual stable isotope analysis in the regulated Colorado River through Grand Canyon National Park, USA, revealed a food web that varied spatially through this arid biome. Down-river enrichment of δ¹³C data was detected across three trophic levels resulting in shifted food webs. Humpack chub δ¹³C and δ¹⁵N values from muscle plugs and fin clips did not differ significantly. Humpback chub and rainbow trout trophic position is positively correlated with standard length indicating an increase in piscivory by larger fishes. Recovery of the aquatic community from impoundment by Glen Canyon Dam and collecting refinements for stable isotope analysis within large rivers are discussed.     

Seasonal variation in natural abundance of δ13C and 15N in Salicornia brachiata Roxb. populations from a coastal area of India

High and fluctuating salinity is characteristic for coastal salt marshes, which strongly affect the physiology of halophytes consequently resulting in changes in stable isotope distribution. The natural abundance of stable isotopes (δ¹³C and δ¹⁵N) of the halophyte plant Salicornia brachiata and physico-chemical characteristics of soils were analysed in order to investigate the relationship of stable isotope distribution in different populations in a growing period in the coastal area of Gujarat, India. Aboveground and belowground biomass of S. brachiata was collected from six different populations at five times (September 2014, November 2014, January 2015, March 2015 and May 2015). The δ¹³C values in aboveground (?30.8 to ?23.6?‰, average: ?26.6?±?0.4?‰) and belowground biomass (?30.0 to ?23.1?‰, average: ?26.3?±?0.4?‰) were similar. The δ¹³C values were positively correlated with soil salinity and Na concentration, and negatively correlated with soil mineral nitrogen. The δ¹⁵N values of aboveground (6.7–16.1?‰, average: 9.6?±?0.4?‰) were comparatively higher than belowground biomass (5.4–13.2?‰, average: 7.8?±?0.3?‰). The δ¹⁵N values were negatively correlated with soil available P. We conclude that the variation in δ¹³C values of S. brachiata was possibly caused by soil salinity (associated Na content) and N limitation which demonstrates the potential of δ¹³C as an indicator of stress in plants.     

Long term changes in the distribution and δ15N values of individual soil amino acids in the absence of plant and fertiliser inputs

The long-term ‘biodegradation’ on soil amino acids was examined in the control plots of ‘42 parcelles’ experiment, established in 1928 at INRA, Versailles (France). None of the plots is cultivated, but is kept free of weeds, and mixed to a depth of 25 cm twice yearly. Topsoil (0–10 cm depth) samples collected in 1929, 1963 and 1997 were subjected to acid hydrolysis (6 N HCl) for comparison. The distribution and δ¹⁵N natural abundance of 20 individual amino acids in the soils were determined, using ion chromatography (IC) and gas chromatography–combustion–isotope ratio mass spectrometry (GC–C–IRMS). The total N and amino acid-N (AA-N), respectively, decreased by 54 % and 73 % in the period from 1929 to 1997. The average N loss was comparable for 1929–1963 (period 1) and 1963–1997 (period 2), but AA-N loss was three times faster in the former period. This significant reduction in total AA-N content was mirrored in the individual amino acids, which decreased by 74 %?±?1 % (ranging 58–89 %) between 1929 and 1997. The bulk δ¹⁵N values generally increased from 1929 to 1997, mainly associated with comparable or even higher increase of δ¹⁵N of the non-AA-N in the soil. The residence time (t _1/2, time in which half of N was lost from a specific soil pool) was ca. 65?±?5 years for the bulk soil, and comparable for periods 1 and 2. However, between periods 1 and 2 it decreased from 128 to 41 years in the non-AA pool, but increased from 59 to 92 years in the AA-N pool. Proline and amino acids that appear early in soil microbial metabolic pathways (e.g. glutamic acid, alanine, aspartic acid and valine) had relatively high δ¹⁵N values. Phenylalanine, threonine, glycine and leucine had relatively depleted δ¹⁵N values. The average δ¹⁵N value of the individual amino acids (IAAs) increased by 1δ unit from 1929 to 1997, associated with a similar rise from 1929 to 1963, and no change thereafter till 1997. However, the δ¹⁵N values of phenylalanine decreased by more than 7δ¹⁵N units between 1929 and 1997. The δ¹⁵N shift of IAAs from 1929 to 1963 and from 1929 to 1997 was not influenced by the relative amount of N remaining compared with the 1929 soil concentrations. The only exception was phenylalanine which showed decreasing δ¹⁵N associated with its decreasing concentration in the soil. We conclude therefore that in the absence of plant and fertiliser inputs, no change in the δ¹⁵N value of individual soil amino acids occurs, hence the original δ¹⁵N values are preserved and diagnostic information on past soil N (cycling) is retained. The exception was phenylalanine, its δ¹⁵N decreased with decreasing concentration from 1929 to 1997, hence it acted as a ‘potential’ marker for the land use changes (i.e. arable cropping to a fallow). The long term biological processing and reworking of residual amino acids resulted in a (partial) stabilisation in the soil, evidenced by reduced N loss and increased residence time of amino acid N during the period 1963–1997.     

Wild Rabbit Host and Some Parasites Show Trophic-Level Relationships for δ13C and δ15N: A First Report

Abstract

We report the first isotopic study of an animal host-parasite system. Parasitic, intestinal nematodes, Graphidium strigosum and Passalurus ambiguus, were ¹⁵N-enriched relative to their host, the European rabbit Oryctolagus cuniculus, while parasitic cestodes, Cittataenia denticulata and Mosgovoyia pectinata, were ¹⁵N-depleted, suggesting different trophic relationships. Host embryos were more similar in their δ¹³C and δ¹⁵N values to maternal muscle than were any of the parasites. Coprophagy, the direct recycling of food by the rabbit eating its own faeces, did not lead to isotopic differences between stomach contents and faeces, suggesting that the major point for isotopic discrimination in lagomorph nitrogen metabolism is in the animal rather than in the gut. We conclude that bulk δ¹³C and δ¹⁵N can reveal valuable new information about host-parasite relationships, and these could be explored further at the biochemical level using compound-specific isotopic analyses.     

Variations of δ15N-Values and Hydrolyzable Amino Acids in Settling Particles in the Ocean

Abstract

The modification of nitrogen isotopic signals during particle sedimentation in the sea is of great interest for the use of sedimentary δ¹⁵N-values as a paleoceanographic tool. The effect of organic matter degradation on such modification was studied by analyzing nitrogen, hydrolyzable amino acids (THAA) and δ¹⁵N-values in a suit of marine settling particles collected from the Bay of Bengal, Indian Ocean, by using time-series sediment traps, and in underlying sediments. The flux of settling particles showed temporal variations which are related to the monsoons, the major climatic feature of this marine region. During high flux periods settling particles are enriched in nitrogenous material that is less degraded and exhibit higher δ¹⁵N-values than particles showing characteristics of degradation. At the sediment surface more than 95% of the settling particulate nitrogen is lost and the δ¹⁵N-values of the residual sedimentary nitrogen are higher than those of settling particles. The observed increase is interpreted to be due to fractionation during degradation of organic matter.     

Experimental plant for simultaneous production of 14N and 15N by 15N/14N exchange in NO,NO2–HNO3 system under pressure

An experimental study on ¹⁴N and ¹⁵N simultaneous separation using the chemical exchange in NO, NO₂–HNO₃ system under pressure is presented. The influence of the pressure and of the interstage 10 M HNO₃ flow rate on the separation of ¹⁴N and ¹⁵N was measured on a packed column with product and waste refluxers. At steady state and 1.8 atm (absolute), the isotopic concentration at the bottom of the separation column was 0.563 at% ¹⁵N, and in the top of the column was 0.159 at% ¹⁵N. The height equivalent to a theoretical plate and interstage 10 M HNO₃ flow rate values, obtained in these experimental conditions, allows the separation of ¹⁴N highly depleted of ¹⁵N and of ¹⁵N at 99 at% ¹⁵N concentration.     

Characterisation of spatial variability and patterns in tree and soil δ13C at forested sites in eastern Canada

Wholistic isotopic studies provide a necessary foundation on which to build conceptual understanding of ecosystem development processes and provide the basis for further isotopic studies at a site or within an ecophysiological region. This study seeks to broadly characterise δ¹³C spatial variability and spatial patterns within soils and canopy tissues at five forest research sites in eastern Canada. We observe consistent and predictable patterns of leaf δ¹³C variation within trees and a consistent offset between woody and leafy tree tissues. Patterns are similar for both hardwoods and softwoods, but overall hardwoods had canopies that were more depleted in ¹³C. Soil carbon δ¹³C enrichment occurred with depth and appeared to vary according to site soil texture. Upper soil δ¹³C was intermediate between leaves and woody tissues, whereas deeper soil values suggested important contributions from more enriched tree tissues, such as persistent woody debris and possibly roots. The relationship between aboveground and belowground signatures suggests functional or developmental differences between study sites.     

Construction of a Quadratic Model for Predicted and Measured Global Solar Radiation in Chile

Global solar radiation data for sites in Chile are analysed and presented in a form suitable for their use in engineering. A new model for monthly average data is developed to predict monthly average global radiation with acceptable accuracy by using actinographic data due to scarcing of pyranometer data. Use of the new quadratic model is proposed because of its relatively wider spectrum of values for Angstrom coefficients ao, al, and a2.     

Spatial variations in larch needle and soil δ15N at a forest–grassland boundary in northern Mongolia

The spatial patterns of plant and soil δ¹⁵N and associated processes in the N cycle were investigated at a forest–grassland boundary in northern Mongolia. Needles of Larix sibirica Ledeb. and soils collected from two study areas were analysed to calculate the differences in δ¹⁵N between needle and soil (Δδ¹⁵N). Δδ¹⁵N showed a clear variation, ranging from ?8?‰ in the forest to ?2?‰ in the grassland boundary, and corresponded to the accumulation of organic layer. In the forest, the separation of available N produced in the soil with ¹⁵N-depleted N uptake by larch and ¹⁵N-enriched N immobilization by microorganisms was proposed to cause large Δδ¹⁵N, whereas in the grassland boundary, small Δδ¹⁵N was explained by the transport of the most available N into larch. The divergence of available N between larch and microorganisms in the soil, and the accumulation of diverged N in the organic layer control the variation in Δδ¹⁵N.     

Isotope (δ13C, δ15N, δ2H) diet–tissue discrimination in African grey parrot Psittacus erithacus: implications for forensic studies

Diet–tissue isotopic relationships established under controlled conditions are informative for determining the dietary sources and geographic provenance of organisms. We analysed δ¹³C, δ¹⁵N, and non-exchangeable δ²H values of captive African grey parrot Psittacus erithacus feathers grown on a fixed mixed-diet and borehole water. Diet–feather Δ¹³C and Δ¹⁵N discrimination values were +3.8?±?0.3?‰ and +6.3?±?0.7?‰ respectively; significantly greater than expected. Non-exchangeable δ²H feather values (?62.4?±?6.4?‰) were more negative than water (?26.1?±?2.5?‰) offered during feather growth. There was no positive relationship between the δ¹³C and δ¹⁵N values of the samples along each feather with the associated samples of food offered, or the feather non-exchangeable hydrogen isotope values with δ²H values of water, emphasising the complex processes involved in carbohydrate, protein, and income water routing to feather growth. Understanding the isotopic relationship between diet and feathers may provide greater clarity in the use of stable isotopes in feathers as a tool in determining origins of captive and wild-caught African grey parrots, a species that is widespread in aviculture and faces significant threats to wild populations. We suggest that these isotopic results, determined even in controlled laboratory conditions, be used with caution.     

Field-deployable measurements of free-living individuals to determine energy balance: fuel substrate usage through δ13C in breath CO2 and diet through hair δ13C and δ15N values

Carbon isotopes of breath CO₂ vary depending on diet and fuel substrate used. This study examined if exercise-induced δ¹³C-CO₂ changes in substrate utilization were distinguishable from baseline δ¹³C-CO₂ variations in a population with uncontrolled diet, and compared hair isotope values and food logs to develop an isotope model of diet. Study participants included nine women with diverse Body Mass Index (BMI), age, ancestry, exercise history, and diet. Breath samples were collected prior to and up to 12?h after a 5- or 10?K walk/run. Indirect calorimetry was measured with a smartphone-enabled mobile colorimetric device, and a field-deployable isotope analyzer measured breath δ¹³C-CO₂ values. Diet was assessed by food logs and δ¹³C, δ¹⁵N of hair samples. Post-exercise δ¹³C-CO₂ values increased by 0.54?±?1.09‰ (1 sd, n?=?9), implying enhanced carbohydrate burning, while early morning δ¹³C-CO₂ values were lower than daily averages (p?=?0.0043), indicating lipid burning during overnight fasting. Although diurnal δ¹³C-CO₂ variation (1.90?±?0.77‰) and participant baseline range (3.06‰) exceeded exercise-induced variation, temporal patterns distinguished exercise from dietary isotope effects. Hair δ¹³C and δ¹⁵N values were consistent with a new dietary isotope model. Notwithstanding the small number of participants, this study introduces a novel combination of techniques to directly monitor energy balance in free-living individuals.