Evaluating the accuracy and reliability of compound-specific carbon isotopic analysis using gas chromatography-combustion-isotope ratio mass spectrometry with the addition of a reduction furnace.

RATIONALE: Gas chromatography-combustion-isotope ratio mass spectrometry (GC/C/IRMS) is widely used for compound-specific carbon isotopic analysis. However, current isotopic analysis systems utilize the GC IsoLink combustion reactor, and independent reduction furnaces are not implemented. Therefore, whether this limitation in furnace use affects the precision of compound-specific carbon isotopic analysis needs to be evaluated. METHODS: We attempted to add a separate reduction furnace to the GC IsoLink interface and compared the δ13 C values of n-alkanes (including C and H elements), fatty acid methyl ester (including C, H, and O elements), caffeine (USGS61 and USGS62, including C, H, O, and N elements), and 9-ethylcarbazole (including C, H, and N elements) before and after the addition of the reduction furnace using the GC IsoLink combustion reactor. RESULTS: For n-alkanes and fatty acid methyl esters, the δ13 C differences between the measured values and their standard values were basically falling within 0.5‰ whether or not an independent reduction furnace was added. However, for the nitrogen-containing compounds (caffeine and 9-ethylcarbazole), the δ13 C differences between the measured values and their standard values were much larger without an independent reduction furnace (1.0-3.71‰ for USGS61, 1.78-2.19‰ for USGS62, and 0.39-1.13‰ for 9-ethylcarbazole) than with a reduction furnace (-0.31-0.68‰ for USGS61, -0.44-0.06‰ for USGS62, and -0.04-0.25‰ for 9-ethylcarbazole). CONCLUSIONS: The addition of an independent reduction furnace had no significant effect on the δ13 C of n-alkanes and fatty acid methyl esters, but it had a significant effect on the δ13 C of nitrogen-containing compounds. It is suggested that GC IsoLink needs an independent reduction furnace to effectively eliminate the interference of NOx on CO2 isotopic determination to improve the accuracy of δ13 C for nitrogen-containing compounds.

Apparent fractionation of hydrogen isotope from precipitation to leaf wax n-alkanes from natural environments and manipulation experiments.

Knowledge of hydrogen isotopic fractionation (ε) of plant leaf waxes is the foundation for applying hydrogen isotope values (δ2H) in environmental reconstructions. In this work, we systematically investigated plant ε values (εalk/precipitation, εalk/soil water, εalk/leaf water and εalk/lake water, representing the isotopic fractionation between plant n-alkane δ2H and precipitation δ2H, soil water δ2H, leaf water δ2H and lake water δ2H) from the natural environments and manipulation experiments. The results show that the εalk/precipitation values of terrestrial plants have large variations (from -190 ‰ to -20 ‰) and become more negative with increasing aridity index. This phenomenon is possibly caused by the δ2H changes in source water (from precipitation to soil water and then to leaf water) during plant leaf wax synthesis under various evapotranspiration conditions in different climatic zones. The rainfall manipulation experiments show that leaf water δ2H values are generally higher than soil water δ2H values, and the latter are higher than precipitation δ2H values. This finding further demonstrates that the evapotranspiration effect on source water δ2H affects the quantification of the leaf wax apparent ε values (εalk/leaf water < Îµalk/soil water < Îµalk/precipitation). The εalk/lake water values of submerged plants display a smaller range (-153 ± 5 ‰) than the εalk/precipitation values of terrestrial plants, which is close to the terrestrial εalk/precipitation values in humid areas. Therefore, the biosynthetic ε value of terrestrial plant leaf waxes is relatively constant (ca. -153 ± 5 ‰), and the observed variable apparent εalk/precipitation values are possibly caused by the varied degree of evapotranspiration effect on the water that plants used in different climatic conditions. This effect should be considered when applying δ2H values of leaf waxes to trace environmental changes.

Discussion on the need for correction during isotopic analysis of nitrogen by the denitrifier method.

The nitrogen and oxygen isotopes of NO3 - are effectively used to trace the main nitrogen sources and migration processes in the atmosphere, water and soil. NO3 - can be converted into N2O by the bacterial denitrification method, which is an advanced method with high sensitivity. However, due to the existence of a small but inevitable blank during the whole experimental process, the N isotopic signal of N2O produced by denitrification superimposes on that of the N blank. Currently, the standard curve correction method is used to correct measured nitrogen isotope results to mitigate blank interference. It has been reported that high variability of the nitrogen isotope results have been produced by the denitrifier method by conducting an interlaboratory comparison of denitrifier methods and other methods on standards and environmental samples, and to reduce this problem, the nitrogen isotope calibration process with a standard curve is examined in depth in this paper, which uses PreCon-GC-IRMS to determine the nitrogen isotopes in N2O. We demonstrate for the first time that reliable results can be obtained without correction for samples with nitrogen isotope composition ranging from -9.9 to 19.5‰, which covers the natural sample range. This study establishes the double test approach for the bacterial denitrification method, ensuring the accuracy and long-term stability of different batches of nitrogen isotope results.

Variation of compound-specific hydrogen isotope ratios under changing temperature program in gas chromatography/thermal conversion/isotope ratio mass spectrometry.

RATIONALE: In recent experiments, we found that compound-specific δ(2)H values can vary as a result of changing the gas chromatography temperature program under common pyrolysis conditions. To achieve better precision, it is necessary to examine the details and find a solution to this problem when using gas chromatography/thermal conversion/isotope ratio mass spectrometry (GC-TC-IRMS) for hydrogen isotope analysis. METHODS: A test was designed to find the possible temperature effect under four different GC temperature ramp rates using n-alkanes (n-C(21), n-C(27), and n-C(31)) and fatty acids (n-C(12), n-C(18), and n-C(24)). The common 'hexane' method was used initially to condition the pyrolysis reactor. Experiments were then carried out using the 'methane condition' method because it was considered to improve pyrolysis efficiency. RESULTS: Under the 'hexane condition' the measured hydrogen isotope ratios of the n-alkanes and n-fatty acids became more positive with increasing GC temperature ramp rate. The ion current intensity of hydrogen also generally increased. However, when the 'methane condition' method was used, the measured δ(2)H values of the n-alkanes and n-fatty acids showed little change under different GC temperature ramp rates. CONCLUSIONS: Higher pyrolysis efficiency could reduce the tailing of the H(2) peak and the related isotopic variations at increased GC temperature ramp rates. In addition, too slow a temperature ramp rate could broaden the peak width and thus increase the background effect and possible isotopic fractionations in the split interface; this could also influence the hydrogen isotope values. We therefore suggest that the appropriate temperature ramp rate is an important factor in improving the precision in analyzing compound-specific hydrogen isotopes.

An evaluation of alumina reaction tube conditioning for high-precision 2H/1H isotope measurements via gas chromatography/thermal conversion/isotope ratio mass spectrometry.

RATIONALE: The condition of the pyrolysis reactor is very important for obtaining stable, precise hydrogen isotopic ratios using gas chromatography/thermal conversion/isotope ratio mass spectrometry (GC/TC/IRMS). However, few studies of the conditioning process have been conducted, and little is known about the best methods for high-precision hydrogen isotope analysis. METHODS: We investigated δ(2)H variations and observed the changes in carbon coating using six different conditioning methods for the pyrolysis alumina tube: (i) no treatment; (ii) conditioning with 4 µL hexane; (iii) conditioning with 2 µL hexane; (iv) conditioning with 2 µL hexane followed by backflushing overnight; (v) conditioning with 10 s of backflushing with methane; (vi) conditioning with 3 s of backflushing with methane. RESULTS: Conditioning the alumina tube can improve the pyrolysis efficiency of organic compounds because a moderate amount of carbon acts as a catalyst in high-temperature regions of the alumina tube. Carbon actually flows in the tube and is difficult to confine to the high-temperature region. Insufficient amounts of carbon in the high-temperature regions lead to incomplete pyrolysis of organic compounds and lower δ(2)H values due to kinetic fractionation of hydrogen isotopes. In contrast, excess hexane or methane can lead to higher δ(2)H values, probably due to enrichment of deuterium in the hydrocarbon residue. CONCLUSIONS: The δ(2)H values obtained by Method 6 are closest to the TC/EA δ(2)H values and are more precise than those obtained by other methods, perhaps because this method introduces a moderate, consistent amount of carbon with each sample injection.

Identification of nitrate sources in the Jing River using dual stable isotopes, Northwest China.

Nitrate (NO3-) contamination has become a dominant international problem in the aquatic environment, so identifying the sources and transformations of NO3- is the basis for improving water quality. Since the Jing River is the largest tributary of the Wei River, to understand its water quality, this study collected surface water samples from the Shaanxi section of the Jing River during the dry season. The potential sources of NO3- were analyzed by hydrochemical and bi-isotopic methods, and the SIAR model was used to estimate the proportional contribution of each source. Results indicated that NO3--N was the main form of inorganic nitrogen in this area, and the average total nitrogen content was 10.23 mg·L-1, which showed that nitrogen pollution was highly serious; the transformation process of nitrogen in this study area was mainly nitrification; The results of Bayesian model showed that manure and sewage contributed to the most NO3- (64.39%) in the dry season, followed by soil nitrogen, which was 26.35%. These results help to adopt better nitrogen management measures to meet the national environmental quality standards for surface water.