• Title/Summary/Keyword: N isotopic fractionation

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Increase in δ15N of Nitrate through Kinetic Isotope Fractionation Associated with Denitrification in Soil

  • Choi, Woo-Jung;Lee, Sang-Mo;Yoo, Sun-Ho
    • Journal of Applied Biological Chemistry
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    • v.44 no.3
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    • pp.135-139
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    • 2001
  • To observe the changes in isotopic composition (${\delta}^{15}N$) of $NO_3{^-}$ during denitrification, an incubation experiment using soil treated with nitrification inhibitor (2-chloro-6-trichloromethyl-pyridine) under water-saturated condition was conducted for 153 h. The $NO_3-N$ concentration decreased from 73.3 to $20.6mg\;kg^{-1}$ during the incubation period, with denitrification rate constant of $0.00905h^{-1}$, and ${\delta}^{15}N$ values of $NO_3-N$ increased from +0.9 to +25.5‰ with decreasing the $NO_3-N$ concentration. The increase in the ${\delta}^{15}N$ values of $NO_3-N$ is due to kinetic isotope fractionation, which always results in $^{15}N$ enrichment of the substrate. The isotopic fractionation factor calculated in this study was 1.0196, an indication that 1.96% more $^{14}NO_3{^-}$ reacted at a given time interval than a comparable number of $^{15}NO_3{^-}$. The ${\delta}^{15}N$ values measured through the incubation study showed a good agreement with the results calculated from the Fochts isotope fractionation model. Our results suggest that when the ${\delta}^{15}N$ of $NO_3{^-}$ is used for tracing the fate of N, the kinetic isotope fractionation associated with denitrification must be taken into consideration.

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Nitrogen Isotope Compositions of Synthetic Fertilizer, Raw Livestock Manure Slurry, and Composted Livestock Manure (화학비료, 가축분뇨 및 퇴비의 질소동위원소비)

  • Lim, Sang-Sun;Lee, Sang-Mo;Lee, Seung-Heon;Choi, Woo-Jung
    • Korean Journal of Soil Science and Fertilizer
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    • v.43 no.4
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    • pp.453-457
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    • 2010
  • To investigate the difference in N isotope ratio ($^{15}N/^{14}N$, expressed as ${\delta}^{15}N$) among N sources (synthetic fertilizer, livestock manure, and manure compost), eight synthetic fertilizer, four livestock manure, and thirty-seven compost samples were collected and analyzed for ${\delta}^{15}N$. The mean ${\delta}^{15}N$ values of N sources were $-1.5{\pm}0.5$‰ (range: -3.9 to +0.5‰) for synthetic fertilizer, $+6.3{\pm}0.4$‰ (+5.3 to +7.2‰) for manure, and $+16.0{\pm}0.4$‰ (+9.3 to +20.9‰) for compost. The lower ${\delta}^{15}N$ of synthetic fertilizer was attributed to its N source, atmospheric $N_2$ of which ${\delta}^{15}N$ is 0‰ Meanwhile, more $^{15}N$-enrichment of compost than manure was assumed to be resulted from N isotopic fractionation (faster loss of $^{14}N$-bearing compound than $^{15}N$) associated with N loss particularly via $NH_3$ volatilization during composting. Therefore, our study shows that ${\delta}^{15}N$ values could successfully serve in discriminating two major N sources (synthetic fertilizer and compost) in agricultural system.

Quantifying nitrogen source contribution ratios using stable isotope method: Application of Bayesian mixing model (안정동위원소를 이용한 하천에서의 질소오염원 기여율 정량화: Bayesian 혼합모델의 적용)

  • Nam, Tae-Hui;Ryu, Hui-Seoung;Kang, Tae-Woo;Han, Yeong-un;Kim, Jihyun;Lee, Kyounghee;Hwang, Soonhong;Kim, Kyunghyun
    • Journal of Korean Society on Water Environment
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    • v.35 no.6
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    • pp.510-519
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    • 2019
  • The 'Stable Isotope Analysis in R' (SIAR), one of the Bayesian mixing models for stable isotopes, has been proven to be useful for source apportionment of nitrates in rivers. In this study, the contribution ratios of nitrate sources were quantified by using the SIAR based on nitrogen and oxygen stable isotope measurements in the Yeongsan River. From the measurements, it was found that the values of δ15N-NO3 and δ18O-NO3 ranged from -8.2 ‰ to +13.4 ‰ and from +2.2 ‰ to +9.8 ‰, respectively. We further analyzed the contribution ratios of the five nitrate sources by using the SIAR. From the modeling results, the main nitrate source was found to be soil N (29.3 %), followed by sewage (26.7 %), manure (19.6 %), chemical fertilizer (17.9 %) and precipitation (6.3 %). From the results, it was found that the anthropogenic sources, i.e., sewage, manure and chemical fertilizer contribute 64.2% of the total nitrate inflow from the watershed. Due to the significant correlation of δ15N-NO3 and lnNO3- in this study, the fractionation factors reflecting the biogeochemical processes of stable isotope ratios could be directly obtained. This may make the contribution ratios obtained in this study more precise. The fractionation factors were identified as +3.64 ± 0.91 ‰ for δ15N-NO3 (p<0.01) and -5.67 ± 1.73 ‰ for δ18O-NO3(p<0.01), respectively, and were applied in using the SIAR. The study showed that the stable isotope method using the SIAR could be applied to quantitatively calculate the contribution ratios of nitrate sources in the Yeongsan River.

Ginseng authenticity testing by measuring carbon, nitrogen, and sulfur stable isotope compositions that differ based on cultivation land and organic fertilizer type

  • Chung, Ill-Min;Lee, Taek-Jun;Oh, Yong-Taek;Ghimire, Bimal Kumar;Jang, In-Bae;Kim, Seung-Hyun
    • Journal of Ginseng Research
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    • v.41 no.2
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    • pp.195-200
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    • 2017
  • Background: The natural ratios of carbon (C), nitrogen (N), and sulfur (S) stable isotopes can be varied in some specific living organisms owing to various isotopic fractionation processes in nature. Therefore, the analysis of C, N, and S stable isotope ratios in ginseng can provide a feasible method for determining ginseng authenticity depending on the cultivation land and type of fertilizer. Methods: C, N, and S stable isotope composition in 6-yr-old ginseng roots (Jagyeongjong variety) was measured by isotope ratio mass spectrometry. Results: The type of cultivation land and organic fertilizers affected the C, N, and S stable isotope ratio in ginseng (p < 0.05). The ${\delta}^{15}N_{AIR}$ and ${\delta}^{34}S_{VCDT}$ values in ginseng roots more significantly discriminated the cultivation land and type of organic fertilizers in ginseng cultivation than the ${\delta}^{13}C_{VPDB}$ value. The combination of ${\delta}^{13}C_{VPDB}$, ${\delta}^{15}N_{AIR}$, or ${\delta}^{34}S_{VCDT}$ in ginseng, except the combination ${\delta}^{13}C_{VPDB}-^{34}S_{VCDT}$, showed a better discrimination depending on soil type or fertilizer type. Conclusion: This case study provides preliminary results about the variation of C, N, and S isotope composition in ginseng according to the cultivation soil type and organic fertilizer type. Hence, our findings are potentially applicable to evaluate ginseng authenticity depending on cultivation conditions.

Contrasting Sources of Plant Wax n-alkanes and n-alkanoic Acids in Gulf of Mexico Sediments (ODP 625B) (멕시코만 코어 퇴적물(ODP 625B)의 식물왁스 탄화수소(n-alkanes)와 지방산(n-alkanoic acids)의 생성기원 비교 연구)

  • Suh, Yeon Jee
    • Ocean and Polar Research
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    • v.41 no.2
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    • pp.89-97
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    • 2019
  • Long chain plant waxes (n-alkanes, n-alkanoic acids, and n-alcohols) and their carbon isotopic compositions (${\delta}^{13}C$) in geologic archives are valuable tools for paleovegetation reconstruction. However, the sensitivity of different plant wax constituents to vegetation shift is not well understood. This study explores controls on the variation in ${\delta}^{13}C$ values of long-chain n-alkanes ($C_{27}$ to $C_{33}$) and n-alkanoic acids ($C_{26}-C_{30}$) in the Gulf of Mexico core sediments (ODP 625B) near the Mississippi River delta. n-Alkanoic acids' ${\delta}^{13}C$ values were higher than those of n-alkanes by 1-2‰ on average and such a pattern is the opposite from their isotope fractionation observed in living plants: 1-2‰ smaller in n-alkanes than n-alkanoic acids. We attribute this offset to contributions from aquatic plants or microbes that produce high concentrations of $^{13}C-enriched$ long-chain n-alkanoic acids. The sensitivity of n-alkanes and n-alkanoic acids to vegetation and climate varied among chain lengths. The $n-C_{33}$ alkanes were most sensitive to $C_4$ grassland expansion among n-alkane homologues, while no specific trend was observed in n-alkanoic acids. This is due to the similarity in n-alkanoic acid concentrations between $C_3$ and $C_4$ plants by homologues and low terrestrial plant-derived n-alkanoic acid contributions to the sediments. The results of this study suggest that long chain n-alkanoic acids' ${\delta}^{13}C$ values in sediments may be influenced by contributions from different sources such as aquatic plants or microbial inputs and therefore interpretations regarding this matter should be cautiously formulated. We suggest that there is a need for further studies on characterizing long-chain n-alkanoic acids ($C_{26}-C_{34}$) in aquatic plants and microbes from various climates and environments in order to investigate their production and integration into sedimentary archives.

Reconstruction of Nitrate Utilization Rate Change Based on Diatom-bound Nitrogen Isotope Values in the Central Slope Area of the Bering Sea during the Early Pleistocene (2.4-1.25 Ma) (플라이스토세 전기(2.4-1.25 Ma) 동안 베링해 중부 대륙사면 지역의 규조 골격내 유기물 질소동위원소 값에 의한 질산염 이용률의 변화 복원)

  • Kim, Sunghan;Khim, Boo-Keun
    • Ocean and Polar Research
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    • v.38 no.3
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    • pp.195-207
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    • 2016
  • Because the high latitude region in the North Pacific is characterized by high primary production in the surface water enriched with nutrients, it is important to understand the variation of surface water productivity and associated nutrient variability in terms of global carbon cycle. Surface water productivity change or its related nutrient utilization rate during the Northern Hemisphere Glaciation (NHG; ca. 2.73 Ma) has been reported, but little is known about such circumstances under gradual climate cooling since the NHG. Bulk nitrogen isotope (${\delta}^{15}N_{bulk}$) of sedimentary organic matter has been used for the reconstruction of nutrient utilization rate in the surface water. However, sedimentary organic matter experiences diagenesis incessantly during sinking through the water column and after burial within the sediments. Thus, in this study we examine the degree of nitrate utilization rate during the early Pleistocene (2.4-1.25 Ma) since the NHG, using the diatom-bound nitrogen isotope (${\delta}^{15}N_{db}$), which is known to be little influenced by diagenesis, from Site U1343 in the Bering slope area. ${\delta}^{15}N_{db}$ values range from ~0.5 to 5.5‰, which is lower than ${\delta}^{15}N_{bulk}$ values, but they vary with larger amplitude. Variation patterns between ${\delta}^{15}N_{db}$ values and biogenic opal concentration are generally consistent, which indicates that the nitrate utilization rate is closely related to opal productivity change in the surface water. A positive correlation between opal productivity and nitrate utilization rate was observed, which is different from the other high latitude regions in the North Pacific. The main reason for this contrasting relationship is that the primary production in the surface water at Site U1343 is influenced mostly by the degree of sea ice formation. Still, although concerns about diagenetic alteration have been avoided by using ${\delta}^{15}N_{db}$, the effects of the preservation state of biogenic opal and the species-dependent isotopic fractionation on ${\delta}^{15}N_{db}$ should be assessed in the future studies.

Stable Carbon and Nitrogen Isotopes of Sinking Particles in the Eastern Bransfield Strait (Antarctica)

  • Khim, Boo-Keun;Kim, Dong-Seon;Shin, Hyoung-Chul;Kim, Dong-Yup
    • Ocean Science Journal
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    • v.40 no.3
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    • pp.167-176
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    • 2005
  • A time-series sediment trap was deployed at 1,034 m water depth in the eastern Bransfield Strait for a complete year from December 25, 1998 to December 24, 1999. About 99% of total mass flux was trapped during an austral summer, showing distinct seasonal variation. Biogenic particles (biogenic opal, particulate organic carbon, and calcium carbonate) account for about two thirds of annual total mass flux $(49.2\;g\;m^{-2})$, among which biogenic opal flux is the most dominant (42% of the total flux). A positive relationship (except January) between biogenic opal and total organic carbon fluxes suggests that these two variables were coupled, due to the surface-water production (mainly diatoms). The relatively low $\delta^{13}C$ values of settling particles result from effects on C-fixation processes at low temperature and the high $CO_2$ availability to phytoplankton. The correspondingly low $\delta^{l5}N$ values are due to intense and steady input of nitrates into surface waters, reflecting an unlikely nitrate isotope fractionation by degree of surface-water production. The $\delta^{l5}N$ and $\delta^{l3}C$ values of sinking particles increased from the beginning to the end of a presumed phytoplankton bloom, except for anomalous $\delta^{l5}N$ values. Krill and the zooplankton fecal pellets, the most important carriers of sinking particles, may have contributed gradually to the increasing $\delta^{l3}C$ values towards the unproductive period through the biomodification of the $\delta^{l3}C$ values in the food web, respiring preferentially and selectively $^{12}C$ atoms. Correspondingly, the increasing $\delta^{l5}N$ values in the intermediate-water trap are likely associated with a switch in source from diatom aggregates to some remains of zooplankton, because organic matter dominated by diatom may be more liable and prone to remineralization, leading to greater isotopic alteration. In particular, the tendency for abnormally high $\delta^{l5}N$ values in February seems to be enigmatic. A specific species dominancy during the production may be suggested as a possible and speculative reason.

Gold-Silver Mineralization in the Kwangyang-Seungju Area (광양-승주지역 금은광상의 광화작용)

  • Lee, Chang Shin;Kim, Yong Jun;Park, Cheon Yong;Ko, Chin Surk
    • Economic and Environmental Geology
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    • v.26 no.2
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    • pp.145-154
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    • 1993
  • Gold-silver deposits in the Kwangyang-Seungju area are emplaced along $N4^{\circ}{\sim}10^{\circ}W$ to $N40^{\circ}{\sim}60^{\circ}W$ trending fissures and fault in Pre-cambrian Jirisan gneiss complex or Cretaceous diorite. Mineral constituents of the ore from above deposits are composed mainly of pyrite, arsenopyrite, pyrrhotite, magnetite, sphalerite, chalcopyrite, galena and minor amount of electrum, tetrahedrite, miargyrite, stannite, covellite and goethite. The gangue minerals are predominantly quartz and calcite. Gold minerals consist mostly of electrum with a 56.19~79.24 wt% Au and closely associated with pyrite, chalcopyrite, miargyrite and galena. K-Ar analysis of the altered sericite from the Beonjeong mine yielded a date of $94.2{\pm}2.4\;Ma$ (Lee, 1992). This indicates a likely genetic tie between ore mineralization and intrusion of the middle Cretaceous diorite ($108{\pm}4\;Ma$). The ${\delta}^{34}S$ values ranged from +1.0 to 8.3‰ with an average of +4.4‰ suggest that the sulfur in the sulfides may be magmatic origin. The temperatures of mineralization by the sulfur isotopic composition with coexisting pyrite-galena and pyrite-chalcopyrite from Beonjeong and Jeungheung mines were $343^{\circ}C$ and $375^{\circ}C$ respectively. This temperature is in reasonable agreement with the homogenization temperature of primary fluid inclusion quartz ($330^{\circ}C$ to $390^{\circ}C$; Park.1989). Four samples of quartz from ore veins have ${\delta}^{18}O$ values of +6.9~+10.6‰ (mean=8.9‰) and three whole rock samples have ${\delta}^{18}O$ values of +7.4~+10.2‰ with an average of 7.4‰. These values are similar with those of the Cretaceous Bulgugsa granite in South Korea (mean=8.3‰; Kim et al. 1991). The calculated ${\delta}^{18}O_{water}$ in the ore-forming fluid using fractionation factors of Bulgugsa et al. (1973) range from -1.3 to -2.3‰. These values suggest that the fluid was dominated by progressive meteoric water inundation through mineralization.

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Isotope Ratio of Mineral N in Pinus Densiflora Forest Soils in Rural and Industrial Areas: Potential Indicator of Atmospheric N Deposition and Soil N Loss (질소공급, 고추의 생육 및 수량에 대한 녹비작물 환원 효과)

  • Kwak, Jin-Hyeob;Lim, Sang-Sun;Park, Hyun-Jung;Lee, Sun-Il;Lee, Dong-Suk;Lee, Kye-Han;Han, Gwang-Hyun;Ro, Hee-Myong;Lee, Sang-Mo;Choi, Woo-Jung
    • Korean Journal of Soil Science and Fertilizer
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    • v.42 no.1
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    • pp.46-52
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    • 2009
  • Deposition of atmospheric N that is depleted in $^{15}N$ has shown to decrease N isotope ratio ($^{15}N/^{14}N$,expressed as ${\delta}^{15}N$) of forest samples such as tree rings, foliage, and total soil-N. However, its effect on ${\delta}^{15}N$ of mineral soil-N which is biologically active N pool has never been tested. In this study, ${\delta}^{15}N$ of mineral N($NH{_4}^+$ and $NO_3{^-}$) in forest soils from organic and two depths of mineral soil layers (0 to 20 cm and 20 to 40cm depth) of Pinus densiflora stands located at two distinct areas (rural and industrial areas) in southern Korea was analyzed to investigate if there is any difference in ${\delta}^{15}N$ of mineral N between these areas. We also evaluated potential N loss of the study sites using ${\delta}^{15}N$ of mineral N. Across the soil layers, the ${\delta}^{15}N$ of $NH{_4}^+$ ranged from +8.9 to +24.8‰ in the rural area and from +4.4 to +13.8‰ in the industrial area. Soils from organic layer (+4.4‰) and mineral layer between 0 and 20 cm (+13.8‰) of industrial area showed significantly lower ${\delta}^{15}N$ of $NH{_4}^+$ than those of rural area (+8.9 and +24.3‰, respectively), probably indicating the greater contribution of $^{15}N$-depleted $NH{_4}^+$ from atmospheric deposition to forest in the industrial area than in the rural area. Meanwhile, ${\delta}^{15}N$ of $NO_3{^-}$ was not different between the rural and industrial areas, probably because ${\delta}^{15}N$ of $NO_3{^-}$ is more likely to be altered by the N loss that causes $^{15}N$ enrichment of the remaining soil N pool. Compared with the ${\delta}^{15}N$ of soil mineral N reported by other studies (from -10.9 to +15.6‰ for $NH{_4}^+$ and -14.8 to +5.6‰ for $NO_3{^-}$), the ${\delta}^{15}N$ observed in our study was substantially high, suggesting that the study sites are more subject to the N loss. It was concluded that $NH{_4}^+$ rather than $NO_3{^-}$ can conserve the ${\delta}^{15}N$ signature of atmospheric N deposition in forest ecosystems.

The Hydrochemical and Stable Isotope Characteristics of Shallow Groundwater Near the Gwangju Stream (광주천 인근 천부 지하수의 수리화학 및 안정동위원소 특성)

  • Yoon, Wook;Ji, Se-Jung;So, Chil-Sub
    • Economic and Environmental Geology
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    • v.36 no.6
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    • pp.441-455
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    • 2003
  • The most common water types are found to be Ca-$HCO_3$, Ca-Na-$HCO_3$ and Ca-Na-$HCO_3$-Cl in Gwangju groundwater. Groundwater near the Gwangju stream are characterized Ca-Cl water type, with over 50 mg/L of C1- and 400 ${\mu}$S/cm of EC. The systematic variation of $Cl^-$, $HCO_3^-$,- EC and ${\gamma}^{18}O$ values in groundwater with distance away from drainages is caused by streamwater infiltration. Stable isotope data indicate that ${\gamma}$D and ${\gamma}^{18}O$ values of groundwaters near drainages were enriched by evaporation effect, showing a equation of ${\gamma}$D=7. 1${\times}{\gamma}^{18}O$-1. ${\gamma}^{18}O$ values over -6${\textperthansand}$ are anomalous in the unconfined groundwater zones, which are influenced by the local surface water enriched in $^{18}O$ composition. Groundwater in highland shows remarkably light ${\gamma}^{18}O$ values below -8$\textperthousand$. The infiltration of streamwater is dominant in unconfined alluvium aquifer near drainages. ${\gamma}^{13}$CDIC values (-17.6∼-15.2$\textperthousand$) of groundwaters near drainages revealed that dissolved inorganic carbon (DIC) is predominantly originated from natural soil-derived $CO_2$. ${\gamma}^{15}N$ and ${\gamma}^{18}O$ values of nitrate are 0∼17.0${\textperthansand}$ and 6.6∼17.4${\textperthansand}$, respectively. Relationship between ${\gamma}^{15}N$ and ${\gamma}^{18}O$ shows a systematic isotopic fractionation caused by denitrification of 40∼60%, suggesting that the major source of groundwater nitrate originated from nitrate of soils, and mixing nitrate of soil and sewage or manure.