Degradation pathways of dissolved carbon in landfill leachate traced with compound-specific 13C analysis of DOC

The isotopic compositions of carbon compounds in landfill leachate provide insights into the biodegradation pathways that dominate the different stages of waste decomposition. In this study, the carbon geochemistry of different carbon pools, environmental stable isotopes and compound-specific isotope analysis (CSIA) of leachate dissolved organic carbon (DOC) fractions and gases show distinctions in leachate biogeochemistry and methane production between the young area of active waste emplacement and the old area of historical emplacement at the Trail Road Landfill (TRL).

The active area leachate has low DOC concentrations (<200 mg l^?1) dominated by fulvic acid (FA=160 mg l^?1), and produces CH₄ dominantly by CO₂ reduction (D? excess=20.6‰). Leachate generated in the area of older waste has high DOC (>4770 mg l^?1) dominated by FA (4482 mg l^?1) and simple fatty acids (acetic=1008 mg l^?1 and propionic=608 mg l^?1), and produces CH₄ by the acetate fermentation pathway (D? excess=9.8‰). CSIA shows an advanced degradation and a progressive accumulation of ¹³C of fatty acids in leachate from the older area. The enriched ¹³C value of FA (?20 and?26‰ for the older and active parts, respectively,) and of low molecular weight DOC (?8 and?27‰) as well as of the bulk DOC (?21 and?25‰) shows more advanced degradation in the older part of the landfill, which is consistent with the shift in the humic/FA ratios (0.05 and 0.18). The ¹³C enrichment of acetate (?12‰) above the ¹³C of DOC (?21‰) and of propionic acid (?19‰), in older leachate, suggests that this acetate has not evolved from the simple degradation of larger organic molecules, but by homoacetogenesis from the enriched dissolved inorganic carbon (DIC) pool (8‰) and H_2, which produce a more enriched ¹³C of acetate. In contrast, the ¹³C of the minor acetate in the active area (?17‰) indicates that CO₂-reducing bacteria must be the primary consumers of H₂, which has resulted in enriched ¹³C_DIC (10‰) and depleted ¹³C_CH4 (?58‰).     

Carbon isotopic signature reveals the geographical trend in methane consumption and production pathways in alpine ecosystems over the Qinghai–Tibetan Plateau

On the Qinghai–Tibetan Plateau, isotopic signatures in soil–atmosphere CH₄ fluxes were investigated in nine grasslands and three wetlands. In the grasslands, the fractionation factor for soil CH₄ uptake, α_soil, was much smaller than the usually reported value of 0.9975–1.0095. Stepwise multiple variation analysis indicates that α_soil is higher for higher soil water contents but is lower for higher C/N ratios of soil surface biomass. In the three wetlands, the soil-emitted δ¹³C–CH₄ was similar (?55.3?±?5.5?‰ and ?53.0?±?5.5?‰) in two bogs separated by >1000?km but was lower (?63.4?±?6.3?‰) in a marsh. Environmental factors related to intrasite variations in soil-emitted δ¹³C–CH₄ include the soil C/N ratio, oxidation–reduction potential, soil C concentration and soil water contents. Geographical isotopic surveys revealed environmental constraints on the CH₄ consumption pathways in grasslands and the biome type-specific consistency in CH₄ production pathways in wetlands.     

Determination of 13C/12C-Ratios in Rumen Produced Methane and CO2 of Cows,Sheep and Camels

Abstract

Naturally produced methane shows different δ¹³C-values with respect to its origin, e.g., geological or biological. Methane-production of ruminants is considered to be the dominant source from the animal kingdom. Isotopic values of rumen methane—given in literature—range between ?80‰ and -50‰ and are related to feed composition and also sampling techniques. Keeping cows, camels and sheep under identical feed conditions and sampling rumen gases via implanted fistulae we compared δ_PDB ¹³C-values of methane and CO₂ between the species. Referring to mean values obtained from 4 or 5 samples at different times of 11 animals (n = 47) we calculated δ_PDB ¹³C-medians resulting in small but not significant differences within and significant differences between the species for CO₂ and methane. The δ_PDB ¹³C-differences between methane and CO₂ were statistically equal within and also between the species. Therefore a linear regression of methane values on CO₂ is appropriate and leads to: δ_PDB ¹³C(methane)‰ = 1,57 * δ_PDB ¹³C(CO₂)‰-47‰ with a correlation coefficient of r = 0,87.     

Field-based cavity ring-down spectrometry of δ13C in soil-respired CO2

Measurement of soil-respired CO₂ at high temporal resolution and sample density is necessary to accurately identify sources and quantify effluxes of soil-respired CO₂. A portable sampling device for the analysis of δ¹³C values in the field is described herein.

CO₂ accumulated in a soil chamber was batch sampled sequentially in four gas bags and analysed by Wavelength-Scanned Cavity Ring-down Spectrometry (WS-CRDS). A Keeling plot (1/[CO₂] versus δ¹³C) was used to derive δ¹³C values of soil-respired CO₂. Calibration to the δ¹³C Vienna Peedee Belemnite scale was by analysis of cylinder CO₂ and CO₂ derived from dissolved carbonate standards. The performance of gas-bag analysis was compared to continuous analysis where the WS-CRDS analyser was connected directly to the soil chamber.

Although there are inherent difficulties in obtaining absolute accuracy data for δ¹³C values in soil-respired CO₂, the similarity of δ¹³C values obtained for the same test soil with different analytical configurations indicated that an acceptable accuracy of the δ¹³C data were obtained by the WS-CRDS techniques presented here. Field testing of a variety of tropical soil/vegetation types, using the batch sampling technique yielded δ¹³C values for soil-respired CO₂ related to the dominance of either C₃ (tree, δ¹³C=?27.8 to?31.9 ‰) or C₄ (tropical grass, δ¹³C=?9.8 to?13.6 ‰) photosynthetic pathways in vegetation at the sampling sites. Standard errors of the Keeling plot intercept δ¹³C values of soil-respired CO₂ were typically<0.4 ‰ for analysis of soils with high CO₂ efflux (>7–9 μmol m^?2 s^?1).     

Measuring δ13C values of atmospheric acetaldehyde via sodium bisulfite adsorption and cysteamine derivatisation

δ¹³C values of gaseous acetaldehyde were measured by gas chromatograph–combustion–isotope ratio mass spectrometer (GC–C–IRMS) via sodium bisulfite (NaHSO₃) adsorption and cysteamine derivatisation. Gaseous acetaldehyde was collected via NaHSO₃-coated Sep-Pak^® silica gel cartridge, then derivatised with cysteamine, and then the δ¹³C value of the acetaldehyde–cysteamine derivative was measured by GC–C–IRMS. Using two acetaldehydes with different δ¹³C values, derivatisation experiments were carried out to cover concentrations between 0.009×10^?3 and 1.96×10^?3 mg·l^?1) of atmospheric acetaldehyde, and then δ¹³C fractionation was evaluated in the derivatisation of acetaldehyde based on stoichiometric mass balance after measuring the δ¹³C values of acetaldehyde, cysteamine and the acetaldehyde–cysteamine derivative. δ¹³C measurements in the derivertisation process showed good reproducibility (<0.5 ‰) for gaseous acetaldehyde. The differences between predicted and measured δ¹³C values were 0.04–0.31 ‰ for acetaldehyde–cysteamine derivative, indicating that the derivatisation introduces no isotope fractionation for gaseous acetaldehyde, and obtained δ¹³C values of acetaldehyde in ambient air at the two sites were distinct (?34.00 ‰ at an urban site versus?31.00 ‰ at a forest site), implying potential application of the method to study atmospheric acetaldehyde.     

Conference Report

Soil from Free-Air Carbon dioxide Enrichment (FACE) plots (FAL, Braunschweig) under ambient air (375 ppm; δ¹³C–CO₂?9.8‰) and elevated CO₂ (550 ppm; for six years; δ¹³C–CO₂?23‰), either under 100% nitrogen (N) (180 kg ha^?1) or 50% N (90 kg ha^?1) fertilisation treatments, was analysed by thermogravimetry. Soil samples were heated up to the respective temperatures and the remaining soil was analysed for δ¹³C and δ¹⁵N by Isotope Ratio Mass Spectrometry (IRMS). Based on differential weight losses, four temperature intervals were distinguished. Weight losses in the temperature range 20–200 °C were connected mostly with water volatilisation. The maximum weight losses and carbon (C) content were measured in the soil organic matter (SOM) pool decomposed at 200–360 °C. The largest amount of N was detected in SOM pools decomposed at 200–360 °C and 360–500 °C. In all temperature ranges, the δ¹³C values of SOM pools were significantly more negative under elevated CO₂ versus ambient CO₂. The incorporation of new C into SOM pools was not inversely proportional to its thermal stability. 50% N fertilisation treatment gained higher C exchange under elevated CO₂ in the thermally labile SOM pool (200–360 °C), whereas 100% N treatment induced higher C turnover in the thermally stable SOM pools (360–500 °C, 500–1000 °C). Mean Residence Time of SOM under 100% N and 50% N fertilisation showed no dependence between SOM pools isolated by increasing temperature of heating and the renovation of organic C in those SOM pools. Thus, the separation of SOM based on its thermal stability was not sufficient to reveal pools with contrasting turnover rates of C.     

Spectral intensities in the ν3 bands of 12CH4 and 13CH4

Relative and absolute line intensities for the ν₃ bands of the ¹²C and ¹³C isotopic varieties of methane have been measured using a tunable difference-frequency laser spectrometer. From these data the integrated band strength of ¹³CH₄ is calculated to be 0.983 ± 0.007 that of ¹²CH₄, with the uncertainty representing three standard deviations. The absolute ν₃ bandstrength for ¹²CH₄ is 266.1 ± 3.0 cm^?2 atm ^?1 at 294.7 K where the errors are dominated by the pressure measurement. This band strength corresponds to an effective transition moment 〈μ₃〉 = 0.0534(3)D for ¹²CH₄ from which the ν₄ band dipole moment and the Herman-Wallis F factor can be estimated using a recent force field model for methane.     

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.     

Characteristics of suspended matter in the River Sava watershed,Slovenia

A combination of C/N ratios, δ¹³C and δ¹⁵N values in suspended matter was used to examine the seasonal (late summer 2004 and spring 2005) relationship with hydrological characteristics of the River Sava watershed in Slovenia. The values of C/N ratios range from 1.2 to 19.1, δ¹³C values range from?29.2 to?23.0 ‰ and δ¹⁵N values from 0.5 to 16.7 ‰ and indicate that the samples are a mixture of two end members: modern soils and plant litter. A simple mixing model was used to indicate that soil organic carbon prevails over plant litter and contributes more than 50% of suspended material. The calculated annual particulate organic carbon flux is estimated as 5.2×10¹⁰ g C/year, the annual particulate nitrogen flux 8.5×10⁹ g N/year and the total suspended solid flux is estimated to be 1.3×10¹² g/year. Anthropogenic impact was detected only in a tributary stream of the River Sava, which is located in an agriculture–industrial area and is reflected in higher δ¹⁵N values in suspended matter and high nitrate concentrations in the late summer season.     

Untersuchungen zur Isotopensignatur von Methan und Kohlendioxid aus biogenen Gasen unterschiedlicher Quellen

Abstract

The isotopic compositions of biogenic carbon dioxide and methane from different sites were investigated. The δ¹³C values of methane vary mainly between ?55‰ and ?75‰ whereas δ¹³C values of carbon dioxide were found from about + 11‰ to ?23‰. Especially the latter ones are not so typical for microbial gases. The different sites don't vary over the whole scales but form certain groups. Secondary effects like diffusion change the δ values of both components in an even more negative direction, while oxidation processes near the surface result in more positive δ¹³C values for methane and very negative δ¹³C values for carbon dioxide.     

Line strength and collisional broadening coefficients of H2O at 2.7 μm for natural gas quality assurance applications

We employed tunable diode laser absorption spectroscopy to measure the line strength, the methane (CH₄), ethane (C₂H₆) and the propane (C₃H₈) broadening coefficients for the 523–422 H₂O transition at 3619.61 cm^?1. Water amount fractions generated by a stable and accurate humidity transfer standard, traceable to the SI units via the German national humidity standard, were used to calibrate the spectroscopic line strength measurements. We focus on the traceability of the measured line data to the SI and on uncertainty assessments following the guidelines of the Guide to the Expression of Uncertainty in Measurement. We determined the line strength to be (8.42 ± 0.07)×10^?20 cm^?1/(cm^?2 molecule) corresponding to a relative uncertainty of ±0.8%. To the best of our knowledge, we report the first methane, ethane and propane broadening coefficients of (8.037 ± 0.056)×10^?5 cm^?1/hPa, (9.077 ± 0.064)×10^?5 cm^?1/hPa and (10.469 ± 0.073)×10^?5 cm^?1/hPa for the 523–422 H₂O transition at 3619.61 cm^?1, respectively. The relative combined uncertainties of the stated CH₄, C₂H₆ and C₃H₈ broadening coefficients are in the ±0.7% range.     

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.     

Biological fractionation of stable Ca isotopes in Göttingen minipigs as a physiological model for Ca homeostasis in humans

In order to investigate fractionation of calcium (Ca) isotopes in vertebrates as a diagnostic tool to detect Ca metabolism dysfunction we analyzed the Ca isotopic composition (δ^44/40Ca?=?[(⁴⁴Ca/⁴⁰Ca)_sample/(⁴⁴Ca/⁴⁰Ca)_reference]?1) of diet, faeces, blood, bones and urine from Göttingen minipigs, an animal model for human physiology. Samples of three groups were investigated: 1. control group (Con), 2. group with glucocorticosteroid induced osteoporosis (GIO) and 3. group with Ca and vitamin D deficiency induced osteomalacia (?CaD). In contrast to Con and GIO whose average δ^44/40Ca_faeces values (0.39?±?0.13‰ and 0.28?±?0.08‰, respectively) tend to be lower than their diet (0.47?±?0.02‰), δ^44/40Ca_faeces of ?CaD (?0.27?±?0.21‰) was significantly lower than their δ^44/40Ca_diet (0.37?±?0.03‰), but also lower than δ^44/40Ca_faeces of Con and GIO. We suggest that the low δ^44/40Ca_faeces of ?CaD might be due to the contribution of isotopically light Ca from gastrointestinal fluids during gut passage. Assuming that this endogenous Ca source is a common physiologic feature, a fractionation during Ca absorption is also required for explaining δ^44/40Ca_faeces of Con and GIO. The δ^44/40Ca_urine of all groups are high (>2.0‰) reflecting preferential renal reabsorption of light Ca isotopes. In Göttingen minipigs we found a Ca isotope fractionation between blood and bones (Δ^44/40Ca_blood-bone) of 0.68?±?0.15‰.     

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.     

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.     

Factors Influencing Stable Isotope Ratios in CH4 and CO2 Within Subenvironments of Freshwater Wetlands: Implications for δ-Signatures of Emissions

Abstract

Much uncertainty still exists regarding spatial and temporal variability of stable isotope ratios (¹³C/¹²C and D/H) in different CH₄-emission sources. Such variability is especially prevalent in freshwater wetlands where a range of processes can influence stable isotope compositions, resulting in variations of up to ～50‰ for δ¹³C-CH₄ and ～150‰ for δD-CH₄ values. Within a temperate-zone bog and marsh situated in southwestern Ontario, Canada, gas bubbles in pond sediments exhibit only minor seasonal and spatial variation in δ¹³C-CH₄, δD-CH₄ and δ¹³C-CO₂ values. In pond sediments, CO₂ appears to be the main source of carbon during methanogenesis either directly via CO₂ reduction or indirectly through dissimilation of autotrophic acetate. In contrast, CH₄ production occurs primarily via acetate fermentation at shallow depths in peat soils adjacent to ponds at each wetland. At greater depths within soils, σCO₂ and H₂O increasingly exert an influence on δ¹³C- and δD-CH₄ values. Secondary alteration processes (e.g., methanotrophy or diffusive transport) are unlikely to be responsible for depth-related changes in stable isotope values of CH₄. Recent models that attempt to predict δD-CH₄ values in freshwater environments from D/H ratios in local precipitation do not adequately account for such changes with depth. Subenvironments (i.e., soil-forming and open water areas) in wetlands should be considered separately with respect to stable isotope signatures in CH₄ emission models.     

Use of cw-CRDS for studying the atmospheric oxidation of acetic acid in a simulation chamber

The coupling between cavity ring-down spectroscopy (CRDS) and an environmental chamber in the investigation of photo-induced reaction mechanisms is demonstrated for the first time. The development of the CRDS device and the corresponding analytical performances are presented. The first application is devoted to the investigation of the branching ratio of the ^?OH radical reaction of CH₃C(O)OH and CH₃C(O)OD under tropospheric conditions. An environmental chamber coupled to two complementary detection systems is used:

gas chromatography with FTIR spectroscopy for quantitative detection of acetic acid;

CRDS for quantitative detection of CO₂.

Investigation of the reaction kinetics of ^?OH+CH₃C(O)OH gives a rate constant of (6.5±0.5)×10^-13 cm³?molecule^-1?s^-1 (296 K) and shows good agreement with literature data. The product study indicates that the H-abstraction channel from the acid group is the dominant pathway with a branching ratio of (78±13)%, whereas the corresponding D-abstraction channel in the ^?OH+CH₃C(O)OD reaction represents only (36±7)%. This result could be attributed to a strong kinetic isotope effect. Glyoxylic acid has also been detected for the first time as by-product. These results illustrate the high interest of the CRDS technique in the investigation of atmospheric relevant problems.     

The relative isotopic abundance (δ13C, δ15N) during composting of agricultural wastes in relation to compost quality and feedstock

Variations in the relative isotopic abundance of C and N (δ¹³C and δ¹⁵N) were measured during the composting of different agricultural wastes using bench-scale bioreactors. Different mixtures of agricultural wastes (horse bedding manure?+?legume residues; dairy manure?+?jatropha mill cake; dairy manure?+?sugarcane residues; dairy manure alone) were used for aerobic–thermophilic composting. No significant differences were found between the δ¹³C values of the feedstock and the final compost, except for dairy manure?+?sugarcane residues (from initial ratio of ?13.6?±?0.2?‰ to final ratio of ?14.4?±?0.2?‰). δ¹⁵N values increased significantly in composts of horse bedding manure?+?legumes residues (from initial ratio of +5.9?±?0.1?‰ to final ratio of +8.2?±?0.5?‰) and dairy manure?+?jatropha mill cake (from initial ratio of +9.5?±?0.2?‰ to final ratio of +12.8?±?0.7?‰) and was related to the total N loss (mass balance). δ¹³C can be used to differentiate composts from different feedstock (e.g. C₃ or C₄ sources). The quantitative relationship between N loss and δ¹⁵N variation should be determined.     

Preparation and comparative structural properties of porous SnO2 microrods and submicrorods

A facile two-step approach has been used for the synthesis of porous SnO₂ rods: the initial room-temperature precipitation of precursor SnC₂O₄ and its subsequent thermal decomposition at 550 °C. Both the as-obtained porous SnO₂ microrods (length ～10.0?±?3.5 μm, diameter ～1.1?±?0.4 μm) and submicrorods (length ～5.8?±?1.9 μm, diameter ～0.4?±?0.1 μm) are the crystalline mixtures of major tetragonal and minor orthorhombic crystal phases, showing a tetragonal fraction of 84.7 and 87.0 %, respectively. When applied as a lithium-ion battery anode, the porous submicrorods (specific surface area ～13.6 m² g^?1) can deliver an initial discharge capacity of 1,730.7 mAh g^?1 with a high coulombic efficiency of 61.6 % and show the 50th discharge capacity of 662.8 mAh g^?1 at 160 mA g^?1 within a narrow potential range of 10.0 mV to 2.0 V. Similarly, even the anode of porous microrods (specific surface area ～11.8 m² g^?1) can still exhibit an initial discharge capacity of 1,661.1 mAh g^?1 at 160 mA g^?1 with a coulombic efficiency of 60.9 %. Regardless of the polymorphic nature, the acquired porosity may only alleviate the huge volume change of anodes for the first cycle; thus, the structural parameters of average size and specific surface area can be feasibly associated with the enhanced lithium storage capability. Anyway, these indicate a facile oxalate precursor method for the controlling synthesis and high performance of rodlike SnO₂ for lithium-ion batteries.     

13C and 15N Abundances in the Sediment Core (VER 92/1-St-10-GC2) from Northern Lake Baikal

Abstract

Carbon and nitrogen stable isotope compositions of organic matter, TOC/TN ratio, and manganese concentration in a sediment core that was collected in northern part of Lake Baikal (VER92ST10-GC2, water depth at 922 m, about 3 m long) were investigated to elucidate the origin of the sedimentary organic matter and its associated environmental factors.

The sediment core was composed of mainly two parts: turbidite sections and other sections. Constant δ¹³C and δ¹⁵N values of the turbidite sections were observed (- 26.8 ±0.2 ‰ for δ¹³C and 3.2 ± 0.1 ‰ for δ¹⁵N) throughout the core. The higher δ¹³C in turbidite sections (about - 27 ‰) than that of the other sections (- 31 to - 29 ‰) was clearly observed, and δ¹⁵N was different between turbidite sections (about 3‰) and other sections (3 to 5 ‰). δ¹³C of other sections was close to that of pelagic phytoplankton, indicating that sediment other than turbidite sections is composed of autochthonous components. The variation of stable isotopes in other sections may be possibly caused by the changes in either phytoplankton growth rate or contribution ratios of terrestrial to aquatic plants for δ¹³C. Either denitrification or fluctuation of δ¹⁵N in pelagic phytoplankton can be the cause of variable δ¹⁵N in other sections.