• 제목/요약/키워드: 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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    • 제44권3호
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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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화학비료, 가축분뇨 및 퇴비의 질소동위원소비 (Nitrogen Isotope Compositions of Synthetic Fertilizer, Raw Livestock Manure Slurry, and Composted Livestock Manure)

  • 임상선;이상모;이승헌;최우정
    • 한국토양비료학회지
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    • 제43권4호
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    • pp.453-457
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    • 2010
  • 화학비료, 가축분뇨 및 퇴비 등 주요 질소원의 질소동위원소비 (${\delta}^{15}N$) 차이를 조사하기 위해 각각 8, 4, 37점의 시료를 채취하여 ${\delta}^{15}N$을 분석하였다. 평균 ${\delta}^{15}N$ 값은 화학비료가 $-1.5{\pm}0.5$‰ (범위: -3.9~+0.5‰‰), 가축분뇨가 $+6.3{\pm}0.4$‰ (+5.3~+7.2‰), 가축분퇴비가 $+16.0{\pm}0.4$‰ (+9.3~+20.9‰)였다. 화학비료가 타 질소원에 비해 ${\delta}^{15}N$ 값이 낮은 것은 화학비료 제조시 이용하는 질소원인 대기 $N_2$${\delta}^{15}N$ 값 (0‰)을 반영하기 때문이다. 반면, 가축분에 비해 퇴비의 ${\delta}^{15}N$ 값이 높은 것은 퇴비화 과정 중 일어나는 질소손실 (특히, 암모니아 휘산)과 관련된 질소동위원소분할효과 ($^{14}N$의 손실속도>$^{15}N$의 손실속도)에 의한 퇴비 중 $^{15}N$ 농축에 의한 결과로 판단된다. 따라서, 본 연구는 ${\delta}^{15}N$ 분석을 통해 현재 우리나라 농업 시스템에서 가장 널리 이용되고 있는 두 가지 질소원 (화학비료와 퇴비)을 구분할 수 있음을 보여준다.

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

  • 남태희;류희성;강태우;한영운;김지현;이경희;황순홍;김경현
    • 한국물환경학회지
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    • 제35권6호
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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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    • 제41권2호
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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.

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

  • 서연지
    • Ocean and Polar Research
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    • 제41권2호
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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.

플라이스토세 전기(2.4-1.25 Ma) 동안 베링해 중부 대륙사면 지역의 규조 골격내 유기물 질소동위원소 값에 의한 질산염 이용률의 변화 복원 (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))

  • 김성한;김부근
    • Ocean and Polar Research
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    • 제38권3호
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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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    • 제40권3호
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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.

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

  • 이창신;김용준;박천영;고진석
    • 자원환경지질
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    • 제26권2호
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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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질소공급, 고추의 생육 및 수량에 대한 녹비작물 환원 효과 (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)

  • 곽진협;임상선;박현정;이선일;이동석;이계한;한광현;노희명;이상모;최우정
    • 한국토양비료학회지
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    • 제42권1호
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    • pp.46-52
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    • 2009
  • 질소동위원소비(${\delta}^{15}N$)가 낮은 대기질소 강하물의 유입에 의해 산림 생태계 내 다양한 시료(나이테, 엽, 토양)의 ${\delta}^{15}N$ 값이 낮아지는 것으로 보고되고 있다. 하지만, 토양 미생물과 식물이 쉽게 이용할 수 있는 토양 무기태 질소의 ${\delta}^{15}N$에 대한 연구는 진행된 바 없다. 본 연구는 대기질소 강하물이 상대적으로 적은 농촌지역과 많은 공업지역에 위치한 적송 산림지역의 유기토양층과 무기토양층(0~20 cm와 20~40 cm) 중 $NH_4{^+}$$NO_3{^-}$${\delta}^{15}N$값을 분석하여 두 지역간의 차이를 조사하였으며, 이들 ${\delta}^{15}N$ 값을 근거로 조사 지역의 질소손실 민감성을 평가하였다. 농촌지역과 공업지역에서 $NH_4{^+}$${\delta}^{15}N$ 값은 각각 +8.9 ~ +24.8‰과 +4.4 ~ +13.8‰로 분포하였다.유기토양층과 무기토양층(0~20 cm)에서 두 지역간 $NH_4{^+}$${\delta}^{15}N$값 차이가 나타났는데, 공업지역에서 각각4.4‰과 +13.8‰이었고, 농촌지역에서는 각각 +8.9‰과 +24.3‰로 공업지역에서 더 낮은 ${\delta}^{15}N$ 값이 나타났다.이는 공업지역에서 ${\delta}^{15}N$값이 낮은 대기 유래 $NH_4{^+}$ 유입량이 더 많았음을 의미한다. 한편, $NO_3{^-}$${\delta}^{15}N$ 값은 지역간 차이가 없었는데, 이는 $NO_3{^-}$가 용탈과 탈질 등에 의해 쉽게 손실되는 과정에서 수반되는 질소동위원소 분할 효과에 의해 강하물에서 유래된 $NO_3{^-}$${\delta}^{15}N$ 기여도가 낮아지기 때문으로 판단된다. 본 연구에서 관측된 무기태 질소의 ${\delta}^{15}N$ 값은 다른 지역에서 조사된 $NH_4{^+}$(-10.9 ~ +15.6‰)과 $NO_3{^-}$(14.8 ~ +5.6‰)의 ${\delta}^{15}N$ 값보다 매우 높은데, 이는 본 연구지역에서 토양 질소 손실 가능성이 높음을 보여준다. 이상의 연구 결과에 의하면 산림토양의 무기태 질소 중 $NO_3{^-}$보다 $NH_4{^+}$이 질소공급원(대기 질소 강하)에 대한 ${\delta}^{15}N$ 정보를 보다 잘 반영하는 것으로 판단된다.

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

  • 윤욱;지세정;소칠섭
    • 자원환경지질
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    • 제36권6호
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    • pp.441-455
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    • 2003
  • 광주지역의 지하수는 주로 Ca-$HCO_3$, Ca-Na-$HCO_3$, Ca-Na-$HCO_3$-Cl 유형의 다양한 수질을 보여준다 그러나 광주천인근 지하수는 50mg/L 이상의 비교적 높은 $Cl^-$농도를 보이고, EC는 400${\mu}s$/cm 이상의 값을 나타내며, Ca-Cl 유형의 수질 특성을 보이고 있다. 일부 지역에서는 하천과 인근 지하수 관정 사이의 거리에 따라서 $Cl^-$, $HCO_3^-$/의 농도, EC와 ${\gamma}^{18}O$ 값이 체계적으로 변화하여 하천수의 지하유입이 확인되고 있다. 안정동위원소 연구결과, 광주지역 전체 지하수의 ${\gamma}^{18}O$ 값의 범위는 -9.2∼-5.5${\textperthansand}$ 이나 광주 동남부 고지대에서는 비교적 가벼운 값(>-8${\textperthansand}$)을 나타내나, 저지대 층적층이 분포된 하천 인근 지하수에서는 -6${\textperthansand}$ 보다 무거운 ${\gamma}^{18}O$ 값이 분포 경향을 보인다. 하천 인근에서 채취된 14개 지하수 시료 사이에는 ${\gamma}$D 및 ${\gamma}^{18}D$ 값이 ${\gamma}D{=}7.1{\times}{\gamma}^{18}O$-1의 관계를 보여 증발작용에 의한 동위원소 비평형을 나타내나, 하천수와 인근 지하수의 ${\gamma}^{18}O$값은 일부 지역에서 하천수 유입에 의한 체계적인 분별효과를 나타내기도 한다. 하천 인근 지하수의 DIC(용존무기탄산염)에 대한 ${\gamma}^{13}C$ 값은 -17.6∼15.2${\textperthansand}$로써 매우 가벼운 값을 나타내며, 토양 유기물 기원의 $CO_2$실 영향이 우세한 것으로 확인되었다. $NO_3^-$에 대한 ${\gamma}^{15}N$${\gamma}^{18}O$ 값은 각 0∼17.0${\textperthansand}$ 및 6.6∼17.4${\textperthansand}$로써 토양의 질산염, 생활하수 및 분뇨 기원의 질소가 혼합된 것으로 나타나고 있으며 대부분 시료는 탈질 화작용이 약 40∼60%까지 진행되면서 ${\gamma}^{15}N$${\gamma}^{18}O$ 값의 체계적인 분별효과가 야기되었다.