The use of stable sulfur and oxygen isotope ratios for interpreting the mobility of sulfate in aerobic forest soils

The isotope compositions of sulfate in bulk precipitation near Munich (Germany) and of seepage water and soil sulfate in five acid forest soils representative of southern Germany were determined in order to ascertain the sources and dynamics of sulfur. While the δ³⁴ S-values of inorganic sulfate in soil solution and solid phases were found to be nearly identical to those of precipitation sulfate, a depletion of several per mil was observed for the δ¹⁸ O-values of sulfate within the uppermost 30 cm of the investigated soils. Mineralization of carbon-bonded sulfur to SO₄²⁻ in the forest floor and humic mineral soil horizons is the only known process which can explain the observed shifts in δ¹⁸O_sulfate. The fact that this¹⁸O-depleted sulfate recharges the groundwater under forests must be considered, when sulfur and oxygen isotope data of sulfate are used for interpretations of the past geochemistry of groundwater systems.Since the δ³⁴S-values of precipitation sulfate were barely altered during percolation through the soils, sulfate mobilities were inferred from a lysimeter experiment with undisturbed soil cores from the same sites, using the stable isotope composition of the irrigation sulfate as a tracer. Fifteen cores of each of the five forest soils, were repeatedly irrigated over 20 months with³⁴S- and¹⁸O-enriched sulfate in three different treatments (35, 63, and 131 kg S ha⁻¹ respectively). Despite the fact that the mean residence time of the seepage water was of the order of only a few months, the throughput of irrigation sulfate did not exceed 34% for all soils and irrigation treatments during the experiment. The low recovery of irrigation sulfate in the seepage water implies mean residence times for sulfur in the uppermost 60 cm of the forest soils of the order of decades, much longer than previously suggested.     

Practical evaluation of carbon sources of forest soils in Slovenia from stable and radio-carbon isotope measurements

Carbon sources were estimated by measuring carbon isotope ratios (??¹³C and ??¹⁴C) with accelerator mass spectrometry (AMS) in forest soils of different lithology. Six locations were selected in temperate deciduous and coniferous stands in Slovenia (?irovski vrh, Idrija, Ko?evski Rog, Pohorje, Gori?nica, and Rakitna), where carbonate rocks consisting of limestone and dolomite are abundant as underlying bedrock. Carbon isotope fractionation would not have occurred in two carbonaceous soils, since the values of both ??¹³C and ??¹⁴C changed consistently in these soils after thermal (550°C, 2?h) or chemical (1?M HCl, 24?h) treatments. Organic components were found to be predominant carbon sources (70?C100%) in the uppermost portions (0?C2?cm in depth). In deeper portions at a depth of about 30?C35?cm, soil carbon may be derived completely from underlying carbonate minerals in Idria, western part of Slovenia. The Combination of heat and chemical treatments with AMS provides practical information on soil carbon sources in carbonaceous soils.     

Effect of organic carbon on the production of biofuel nitrous oxide during the denitrification process

The carbon source plays an important role in denitrification for nitrogen removal from wastewater. In this study, the denitrification performance and nitrous oxide (N₂O) generation in four sequencing batch reactors (SBRs) fed with methanol, ethanol, sodium acetate and glucose were investigated. The maximum N₂O generation was achieved when glucose was used as the carbon source, with a N₂O conversion ratio of 56%. The high conversion ratio was contributed from the organic carbon of glucose and the glucose-acclimated denitrifiers. The nitrite accumulation and N₂O generation during denitrification with glucose as the carbon source increased with increasing chemical oxygen demand to nitrogen ratios in the range of 2–8. The microbial community and their relative abundances varied greatly in the four reactors, and a low abundance of Thauera was found in the glucose-fed SBR, which might contribute to the greater N₂O production. Practical strategies for N₂O generation from the denitrification process using glucose as the carbon source were proposed so as to achieve energy recovery from nitrogen in wastewater.     

Estimation of N2O emission from tea garden soils, their adjacent vegetable garden and forest soils in eastern China

The objective of this study was to investigate nitrous oxide (N₂O) emissions from different land-use types in eastern China. The dynamic changes of N₂O emissions were investigated in tea gardens with different nitrogen application rates, their adjacent vegetable garden and forest soils from June 2009 to May 2010. The results showed that high nitrogen application in a tea garden significantly increased soil N₂O emissions. Lower N₂O emission and percentage of N₂O–N to the applied N were observed in a tea garden with low N application than that from vegetable garden, indicating reasonable control of N application can efficiently decrease N₂O pollution in tea gardens. Both air and soil temperature had significant and positive impact on N₂O emissions, but little effect of precipitation was observed. Therefore, N application rate and environmental temperature are the most essential factors in influencing N₂O emission and should be taken into consideration in the field management of tea production.     

Reformulated O correction of mass spectrometric stable isotope measurements in carbon dioxide and a critical appraisal of historic ‘absolute’ carbon and oxygen isotope ratios

Mass-spectrometric stable isotope measurements of CO₂ use molecular ion currents at mass-to-charge ratios m/z 44, 45 and 46 to derive the elemental isotope ratios n(¹³C)/n(¹²C) and n(¹⁸O)/n(¹⁶O), abbreviated ¹³C/¹²C and ¹⁸O/¹⁶O, relative to a reference. The ion currents have to be corrected for the contribution of ¹⁷O-bearing isotopologues, the so-called ‘¹⁷O correction’. The magnitude of this correction depends on the calibrated isotope ratios of the reference. Isotope ratio calibrations are difficult and are therefore a matter of debate. Here, I provide a comprehensive evaluation of the existing ¹³C/¹²C (¹³R), ¹⁷O/¹⁶O (¹⁷R) and ¹⁸O/¹⁶O (¹⁸R) calibrations of the reference material Vienna Standard Mean Ocean Water (VSMOW) and CO₂ generated from the reference material Vienna Pee Dee Belemnite (VPDB) by reaction with 100% H₃PO₄ at 25 °C (VPDB-CO₂). I find , ¹⁸R_VSMOW/10⁻⁶ = 2005.20 ± 0.45, ¹³R_VPDB-CO2/10^-6= 11124 ± 45, and ¹⁸R_VPDB-CO2/10^-6=2088.37±0.90. I also rephrase the calculation scheme for the ¹⁷O correction completely in terms of relative isotope ratio differences (δ values). This reveals that only ratios of isotope ratios (namely, ¹⁷R/¹³R and ¹³R¹⁷R/¹⁸R) are required for the ¹⁷O correction. These can be, and have been, measured on conventional stable isotope mass spectrometers. I then show that the remaining error for these ratios of isotope ratios can lead to significant uncertainty in the derived relative ¹³C/¹²C difference, but not for¹⁸O/¹⁶O. Even though inter-laboratory differences can be corrected for by a common ‘ratio assumption set’ and/or normalisation, the ultimate accuracy of the ¹⁷O correction is hereby limited. Errors of similar magnitude can be introduced by the assumed mass-dependent relationship between ¹⁷O/¹⁶O and ¹⁸O/¹⁶O isotope ratios. For highest accuracy in the ¹³C/¹²C ratio, independent triple oxygen isotope measurements are required. Finally, I propose an experiment that allows direct measurement of ¹³R¹⁷R/¹⁸R.     

N and O isotope effects during nitrate assimilation by unicellular prokaryotic and eukaryotic plankton cultures

In order to provide biological systematics from which to interpret nitrogen (N) and oxygen (O) isotope ratios of nitrate (¹⁵N/¹⁴N, ¹⁸O/¹⁶O, respectively) in the environment, we previously investigated the isotopic fractionation of nitrate during its assimilation by mono-cultures of eukaryotic algae (Granger et al., 2004). In this study, we extended our analysis to investigate nitrate assimilation by strains of prokaryotic plankton. We measured the N and O isotope effects, ¹⁵ε and ¹⁸ε, during nitrate consumption by cultures of prokaryotic strains and by additional eukaryotic phytoplankton strains (where ε is the ratio of reaction rate constants of the light vs. heavy isotopologues, ^lightk and ^heavyk; ε = ^lightk/^heavyk − 1 × 1000, expressed in per mil). The observed ¹⁵ε ranged from 5‰ to 8‰ among eukaryotes, whereas it did not exceed 5‰ for three cyanobacterial strains, and was as low as 0.4‰ for a heterotrophic α-protoeobacterium. Eukaryotic phytoplankton fractionated the N and O isotopes of nitrate to the same extent (i.e., ¹⁸ε ∼ ¹⁵ε). The ¹⁸ε:¹⁵ε among the cyanobacteria was also ∼1, whereas the heterotrophic α-proteobacterial strain, which showed the lowest ¹⁵ε, between 0.4‰ and 1‰, had a distinct ¹⁸ε:¹⁵ε of ∼2, unlike any plankton strain observed previously. Equivalent N vs. O isotope discrimination is thought to occur during internal nitrate reduction by nitrate reductase, such that the cellular efflux of the fractionated nitrate into the medium drives the typically observed ¹⁸ε:¹⁵ε of ∼1. We hypothesize that the higher in the ¹⁸ε:¹⁵ε of the α-proteobacterium may result from isotope discrimination by nitrate transport, which is evident only at low amplitude of ε. These observations warrant investigating whether heterotrophic bacterial assimilation of nitrate decreases the community isotope effects at the surface ocean.     

Modelling nitrogen and oxygen isotope fractionation during denitrification in a lacustrine redox-transition zone

The stable isotope composition (δ¹⁵N and δ¹⁸O) of nitrate was measured during Summer 1999 in the anaerobic hypolimnion of eutrophic Lake Lugano (Switzerland). Denitrification was demonstrated by a progressive nitrate depletion coupled to increasing δ¹⁵N and δ¹⁸O values for residual nitrate. Maximum δ¹⁵N and δ¹⁸O values amounted to 27.2 and 15.7‰, respectively.¹⁵N and ¹⁸O enrichment factors for denitrification (ε) were estimated using a closed-system model and a dynamic diffusion-reaction model. Using the Rayleigh equation (closed-system approach), we obtained ε values of −11.2 and −6.6‰ for nitrogen and oxygen, respectively. The average ε values derived using the diffusion-reaction model were determined to be −20.7 ± 3.8 for nitrogen and −11.0 ± 1.7 for oxygen. Both N and O isotope fractionation appeared to be lower when denitrification rates where high, possibly in association with high organic carbon availability. In addition, variations in the isotope effects may be attributed to the variable importance of sedimentary denitrification having only a small isotope effect on the water column. The combined measurement of N and O isotope ratios in nitrate revealed that coupled nitrification-denitrification in the open-water was of minor importance. This is the first study of nitrogen and oxygen isotope effects associated with microbial denitrification in a natural lake. Moreover, this study confirms the high potential of δ¹⁸O of nitrate as a valuable biogeochemical tracer in aquatic systems, complementing nitrate δ¹⁵N.     

Calculation of equilibrium stable isotope partition function ratios for aqueous zinc complexes and metallic zinc

The goal of this study is to determine reduced partition function ratios for a variety of species of zinc, both as a metal and in aqueous solutions in order to calculate equilibrium stable isotope partitioning. We present calculations of the magnitude of Zn stable-isotope fractionation (^66,67,68Zn/⁶⁴Zn) between aqueous species and metallic zinc using measured vibrational spectra (fit from neutron scattering studies of metallic zinc) and a variety of electronic structure models. The results show that the reduced metal, Zn(0), will be light in equilibrium with oxidized Zn(II) aqueous species, with the best estimates for the Zn(II)-Zn(0) fractionation between hexaquo species and metallic zinc being Δ^66/64Zn_aq-metal ∼ 1.6‰ at 25 °C, and Δ^66/64Zn_aq-metal ∼ 0.8‰ between the tetrachloro zinc complex and metallic zinc at 25 °C using B3LYP/aug-cc-pVDZ level of theory and basis set. To examine the behavior of zinc in various aqueous solution chemistries, models for Zn(II) complex speciation were used to determine which species are thermodynamically favorable and abundant under a variety of different conditions relevant to natural waters, experimental and industrial solutions. The optimal molecular geometries for [Zn(H₂O)₆]²⁺, [Zn(H₂O)₆]·SO₄, [ZnCl₄]²⁻ and [Zn(H₂O)₃(C₃H₅O(COO)₃)]⁻ complexes in various states of solvation, protonation and coordination were calculated at various levels of electronic structure theory and basis set size. Isotopic reduced partition function ratios were calculated from frequency analyses of these optimized structures. Increasing the basis set size typically led to a decrease in the calculated reduced partition function ratios of ∼0.5‰ with values approaching a plateau using the aug-cc-pVDZ basis set or larger. The widest range of species were studied at the B3LYP/LAN2DZ/6-31G^∗ level of theory and basis-set size for comparison. Aqueous zinc complexes where oxygen is bound to the metal center tended to have the largest reduced partition function ratios, with estimated fractionations ranging from 2.2 to 2.9‰ (⁶⁶Zn/⁶⁴Zn) at 25 °C relative to metallic zinc. The tetrahedrally coordinated tetrachloro zinc complex, where zinc is bound exclusively to chloride, had the lowest reduced partition function ratio for a Zn(II) species (Δ^66/64Zn_aq-metal ∼ 1-1.3‰ at 25 °C). Increasing the number of waters in the second shell of solvation of the above complexes led to variable results, most commonly leading to a decrease of ∼0.2 to 0.3‰ in calculated Δ^66/64Zn_aq-metal at 25 °C.These estimates are useful in the interpretation of observed fractionations during the electrochemical deposition of zinc, where aqueous-metal fractionations of up to 5.5‰ are observed. The models show these are not caused by an equilibrium fractionation process. These results suggest that the redox cycle of zinc during industrial processing may be responsible for isotopically distinct reservoirs of zinc observed in polluted environments. The leaching of metallic zinc or zinc tailings from industrial sites could lead to the observed heavy signature in river systems, the magnitude of which will be reliant on the source material and the aqueous species that form.     

Tracking the fate of dung-derived carbohydrates in a temperate grassland soil using compound-specific stable isotope analysis

Carbohydrates are major organic components of dung and are likely to contribute substantially to increased carbon stocks in manured soils. To investigate this hypothesis, a field-scale experiment was conducted on a temperate grassland site in Devon, UK. C₄ dung (bulk δ¹³C value ?12.6‰) was applied to a temperate grassland C₃ soil (bulk δ¹³C value ?30.3‰) in April and the surface soil beneath cow pats sampled at seven dates over a year. Total carbohydrates were extracted as their monosaccharide components and analysed as the alditol acetates using gas chromatography. The δ¹³C values of the major monosaccharides glucose (?11.5 ±0.6‰), xylose (?10.4 ±0.4‰), arabinose (?10.4 ±0.5‰) and galactose (?8.3 ±1.6‰) extracted from the C₄ dung via acid hydrolysis were indicative of their source. Their weighted mean δ¹³C value was ?10.8‰, 1.8‰ more ¹³C-enriched than the bulk dung value. The δ¹³C values of individual monosaccharides recovered by acid hydrolysis in the 0–1 cm and 1–5 cm soil horizons beneath C₄ cow pats, compared with control soils determined over 372 days, allowed assessment of the extent of incorporation and fluxes of dung-derived monosaccharides. A maximum of 60% of the dung C in soil was derived from carbohydrates after 56 days, declining to around 20% after 372 days. Incorporation dynamics varied between monosaccharide species. Glucose, xylose and arabinose behaved in a similar manner because of their predominantly plant cell wall derived provenance in the dung, whilst dung-derived galactose and mannose appeared to have a microbial source in the soil. The dynamics of total dung-derived monosaccharides in the top 5 cm was comparable to incorporation and flux of bulk dung C, previously estimated using bulk δ¹³C values. The movement of dung-derived carbohydrates into the soil was inequivalent between the 0–1 cm and 1–5 cm horizons. The lack of a significant difference in concentration, but the evidence for the persistence of dung-derived monosaccharides in soil based on δ¹³C values, indicated replacement of existing pools in the soil, suggesting that the ability of this particular soil to sequester further C derived from carbohydrates was limited.     

Modelling the biogeochemical cycle of silicon in soils: Application to a temperate forest ecosystem

We investigated the biogeochemical cycling of silicon (Si) in an acidic brown soil covered by a coniferous forest (Douglas fir). Based on published and original data, we constructed a conceptual model and used a modified version of the reactive transport code MIN3P for model testing and quantification purposes. The model was first calibrated and further validated with respect to biomass data and Si-concentrations in capillary solutions, which were collected monthly over several years by means of suction-cup lysimeters placed at different soil depths.Following sensitivity tests, the model was calibrated quite accurately (limited to a 10% concentration error) by the adjustment of kinetic constants, longitudinal dispersion, and apparent activation energy for K-feldspar dissolution. Calibrated parameter values were constrained by ranges reported in the literature, when available. Mass balance calculations indicate that an average of 60% of the biogeochemical cycle of Si was controlled by biological processes (i.e. Si-uptake and dissolution of phytoliths). Sensitivity analyses suggest that no more than 55% of the Si-cycle is controlled by weathering of primary silicates. Such a large contribution of biological turnover to Si-cycling may be explained by the combined effects of a relatively large Si-content in the litter fall (i.e. specifically in the needles) and high biomass productivity of the coniferous species considered. In addition to potential implications for the global Si cycle, this investigation raises several fundamental questions concerning the nature of Si-uptake mechanisms and physiological use of Si by trees in natural systems.     

The isotopic ratios O/O and O/O in molecular oxygen and their significance in biogeochemistry

Recently, a new method has been introduced for the estimation of photosynthetic oxygen production from the triple isotope composition (δ¹⁷O and δ¹⁸O) of dissolved O₂ in the ocean and of air O₂ in ice cores. This method is based on the deviations (¹⁷Δ) from mass dependent respiratory fractionation, the major process affecting the isotopic composition of air O₂. To apply this method, the slope in the ¹⁷O/¹⁶O vs. ¹⁸O/¹⁶O relationship used for ¹⁷Δ calculation must be known with high accuracy. Using numerical simulations and closed system experiments, we show how the respiratory slope is manifested in the ¹⁷Δ of O₂ in situations where respiration is the only process affecting oxygen isotopic composition (kinetic slope), and in systems in steady state between photosynthesis and respiration (steady state slope). The slopes of the fractionation line in these two cases are different, and the reasons of this phenomenon are discussed. To determine the kinetic respiratory slope for the dominant O₂ consumers in aquatic systems, we have conducted new experiments using a wide range of organisms and conditions and obtained one universal value (0.5179 ± 0.0006) in ln(δ¹⁷O + 1) vs. ln(δ¹⁸O + 1) plots. It was also shown that the respiratory fractionations under light and dark are identical within experimental error. We discuss various marine situations and conclude that the kinetic slope 0.518 should be used for calculating ¹⁷Δ of dissolved O₂. In contrast, a steady state fractionation slope should be used in global mass balance calculations of triple isotope ratios of O₂ in air records of ice cores.     

Stable Cu isotope fractionation in soils during oxic weathering and podzolization

Copper stable isotope ratios are fractionated during various biogeochemical processes and may trace the fate of Cu during long-term pedogenetic processes. We assessed the effects of oxic weathering (formation of Cambisols) and podzolization on Cu isotope ratios (δ⁶⁵Cu). Two Cambisols (oxic weathered soils without strong vertical translocations of soil constituents) and two Podzols (soils showing vertical translocation of organic matter, Fe and Al) were analyzed for Cu concentrations, partitioning of Cu in seven fractions of a sequential extraction and δ⁶⁵Cu values in bulk soil. Cu concentrations in the studied soils were low (1.4-27.6 μg g⁻¹) and Cu was mainly associated with strongly bound Fe oxide- and silicate-associated forms. Bulk δ⁶⁵Cu values varied between −0.57‰ and 0.44‰ in all studied horizons. The O horizons had on average significantly lighter Cu isotope compositions (−0.21‰) than the A horizons (0.13‰) which can either be explained by Cu isotope fractionation during cycling through the plants or deposition of isotopically light Cu from the atmosphere. Oxic weathering without pronounced podzolization in both Cambisols and a weakly developed Podzol (Haplic Podzol 2) caused no significant isotope fractionation in the single profiles, while a slight tendency to lower δ⁶⁵Cu values with depth was visible in all four profiles. This is the opposite depth distribution of δ⁶⁵Cu values to that we observed in hydromorphic soils (soils which show indication of redox changes because of the influence of water saturation) in a previous study. In a more pronounced Podzol (Haplic Podzol 1), δ⁶⁵Cu values and Cu concentrations decreased from Ah to E horizons and increased again deeper in the soil. Humus-rich sections of the Bhs horizon had higher Cu concentrations (2.8 μg g⁻¹) and a higher δ⁶⁵Cu value (−0.18‰) than oxide-rich sections (1.9 μg g⁻¹, −0.35‰) suggesting Cu translocation between E and B horizons as organo-Cu complexes. The different depth distributions in oxic weathered and hydromorphic soils and the pronounced vertical differences in δ⁶⁵Cu values in Haplic Podzol 1 indicate a promising potential of δ⁶⁵Cu values to improve our knowledge of the fate of Cu during long-term pedogenetic processes.     

Effects of tree species and soil depths on ethylene and methane consumption in tropical and temperate forest soils

To date our knowledge is limited with regard to the responses of ethylene and methane consumption by forest soils to tree species and soil types, and to the effect of presence of ethylene on atmospheric methane consumption. The soils at depths from tropical and temperate forests in China were used to study the responses of ethylene and methane consumption to tree species and soil types. The ethylene and methane consumption by soils beneath each forest floor was measured under the same oxic conditions, along with main properties of forest soils. The accumulation of ethylene was studied in the soil slurry （soil/water, 1/2.5）. In temperate soils under spruce and birch forests, maximal consumption rates of ethylene and methane were observed in the 2.5-5.0 cm and 5.0-7.5 cm soil layers, respectively （P〈0.05）. However, a maximal consumption of both occurred in the 0-2.5 cm soil layer under temperate Korean pine forest （P〈0.05）. Contrary to temperate forest soils, there was a significant lower consumption of ethylene and methane in tropical forest soils at less than 20 cm depths under a seasonal rainforest and secondary rubber forest （P〈0.05）. Hence, the potential of ethylene and methane consumption in the 0-20 cm soil profile was variable with tree species and soil types. According to ethylene formation in the soil slurry, there was greater accumulation of ethylene in the 0-2.5 cm soil under temperate forests than under tropical forests, and its accumulation under spruce and birch forests was more than under Korean pine forest （P〈0.05）. The presence of extrinsic ethylene can significantly inhibit the consumption of atmospheric methane by forest soils.     

Vertical patterns of stable carbon isotope in soils and particle-size fractions of karst areas, Southwest China

Taking limestone soil and yellow soil, the two major soil types in karst areas as examples, analyzing stable carbon isotope composition (δ¹³C value) of soil organic matter (SOM) in bulk soils and particle-size fractions of four soil profiles under three vegetable forms, the following results are reached: in the limestone soil profile, soil organic carbon contents are all above 1.0%, the highest value is 7.1% in the surface soil; however, they are between 0.3% and 4.6% in the three yellow soil profiles. From the surface to the bottom of the soil profiles, the variation of δ¹³C value of soil organic carbon for limestone soil profile is only between −24.1‰ and −23.0‰, however, it’s between −24.8‰ and −21.1‰ for yellow soil profiles. The variation range of δ¹³C value of soil organic carbon associated with particle-size separates is slight for limestone soil but is considerable for yellow soil. The contrast research indicates that the changes between the contents and the δ¹³C value of soil organic carbon with depth are complex. The vertical patterns of stable carbon isotope in soil organic matter have a distinct regional characteristic in karst areas.     

Carbon isotope and C/N ratios of suspended matter in rivers: an indicator of seasonal change in C4/C3 vegetation

A combination of δ ¹³C values with C/N ratios in suspended matter has been used to examine the seasonal relationship between C₄ and C₃ vegetation along the Loess Plateau, NW China. The C isotopic composition of suspended organic matter in rivers, together with C/N ratios can differentiate between soil and plant material, and can be used to estimate the relative contributions of soil organic C and plant litter to the suspended matter. The relationship between C isotopic composition and C/N ratios indicates that the samples are a mixture of two end members: (1) modern soils with relatively constant δ ¹³C values, low C content and low C/N ratios; (2) plant litter with varying δ ¹³C values, high C content and high C/N ratios. The results reflect the seasonal distribution of C₄/C₃ vegetation within the area studied, as part of the Loess Plateau. The abundance of C₄ grasses is about 20% for the current summer vegetation ecosystem in the eastern part of the Loess Plateau. Hence, the use of δ ¹³C values and C/N ratios of suspended matter in rivers and modern soil may be useful for reflecting seasonal distribution of C₄/C₃ vegetation in catchments. This could be a useful tool for distinguishing between catchments for GIS studies, and long term planning for ecological management of catchment areas.     

Contemporary lead concentration and stable lead isotope ratio distribution in forest moss across the Czech Republic

Lead concentrations and stable lead isotopes (²⁰⁴Pb, ²⁰⁶Pb, ²⁰⁷Pb, ²⁰⁸Pb) were measured in forest moss samples (Pleurozium schreberi or Scleropodium purum) collected at 273 sites across the Czech Republic during 2010. Continuously decreasing median Pb concentrations in moss were documented over the last two decades: 1995: 11 mg/kg, 2000: 5.66 mg/kg, 2005: 4.94 mg/kg and 2010: 2.85 mg/kg. Several local anomalies have decreased in scale, the overall regional distribution patterns remained, however, the same. The regional Pb isotope ratio distributions show that the ratios show little variation for a large central part of the country and provide the large-scale background isotope ratios for the Czech Republic of about ²⁰⁴Pb/²⁰⁶Pb = 0.0550, ²⁰⁶Pb/²⁰⁷Pb = 1.167, ²⁰⁶Pb/²⁰⁸Pb = 0.478 and ²⁰⁷Pb/²⁰⁸Pb = 0.409 for 2010. This background Pb isotope ratio signal in moss has been locally (900–7500 km²) modified by specific Pb isotopic ratio signals caused by deposition of Pb emissions from known local anthropogenic Pb emission sources, such as industrial combustion of local coal, and a variety of industrial enterprises (metallurgical, engineering and glass works). At some sites where mining of uranium and polymetallic ores took place the moss samples show also a locally specific Pb isotope signal. The in terms of area affected largest deviations in the Pb-isotope ratios, e.g., in the Bohemian Massif, may be due to the input of geogenic dust.     

A reconnaissance study of stable isotope ratios in archaean rocks from the yilgarn block,Western Australia

Isotopic compositions of sulphur, carbon, and oxygen have been determined for constituents from a total of 103 samples of sedimentary rocks, mafic and ultramafic igneous rocks, nickel ores, and gold ores from the Archaean Yilgarn Block.

Sulphides in the bulk of the sedimentary rocks have δ³⁴S values close to 0‰ and appear to have precipitated from solutions which incorporated magmatic sulphur (either juvenile or derived from older rocks). There is no evidence for widespread sulphate reduction.

δ³⁴S values of sulphides in the nickel deposits and associated mafic/ultramafic igneous rocks are within the magmatic range. The small, high‐grade deposits of the Kambalda‐Nepean‐Scotia type have small positive δ³⁴S values, and the large, low‐to‐medium grade dunite‐associated deposits of the Mount Keith‐Perseverance type have small negative δ³⁴S values.

Sulphides in the Kalgoorlie gold ores are enriched in ³²S relative to those in their host dolerite, supporting an epigenetic origin for the gold, under moderately high fO₂ conditions.

The δ¹³C values do not provide unequivocal evidence for the source(s) of the reduced carbon (kerogen) in the sedimentary rocks. Whilst they are compatible with biogenic derivation, it is not possible to rule out contributions from pre‐biotic organic ‘soup’ or from hydrothermal solutions of deep‐seated origin.

Carbonate in the sedimentary rocks are predominantly in epigenetic, sulphide‐bearing veinlets. In many cases, their δ¹³C values suggest precipitation from hydro‐thermal solutions containing magmatically derived CO₂. In only two samples are the petrographic features and δ¹³C values compatible with marine carbonates. Talc‐carbonate altered ultramafic igneous rocks have δ¹³C values consistent with their incorporation of magmatically derived CO₂.

The ?δ¹³C (carbonate‐kerogen) values for most of the sedimentary rock studied fall in a narrow range around +10‰, suggesting isotopic exchange between oxidized and reduced carbon species at moderately high temperatures (>250°C).

δ¹⁸O values of carbonate from both sedimentary rocks and igneous rocks are mainly within the range +7.2‰ to +18.0‰. If the values are primary they are consistent with the formation of carbonate from hydrothermal solutions of magmatic and/or metamorphic origin. However, it is also possible the δ¹⁸O values are the result of post‐depositional equilibration with meteoric waters.     

乙烷稳定碳同位素动力学模拟及地质应用

详细介绍了限定体系下乙烷稳定碳同位素动力学模拟过程及煤成乙烷的同位素演化规律。地质模拟结果展示,煤成天然气乙烷演化规律与甲烷类似,低熟阶段存在一个下降的趋势,其最轻同位素值为-27.8‰,与我国常用的煤成气判别标准基本一致,对应有机质成熟度(Easy%Ro)为1.0。随后,乙烷稳定碳同位素逐渐变重,与Ro之间呈良好的线性关系。