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1 Res. Org. Geochem. 26, (2010) / EA/IRMS * ** *** Abstract ontinuous-flow (on-line) system has revolutionized the study of natural stable isotope variations in organic matter and organic compounds. In particular, carbon and nitrogen isotope analysis of bulk samples using elemental analyzer/isotope ratio mass spectrometer (EA/IRMS) has been widely used in various field of studies, which allows a simple and rapid analysis of the isotope ratios for all types of organic and a wide range of inorganic samples, with a small amount of sample materials compared to the traditional off-line Dual-Inlet method. However, stability, accuracy, and precision on the observed isotope ratios strongly reflect various factors associated with continuousflow system, such as peak intensity (i.e., sample weight), memory effect, and He dilution ratio. Unfortunately, the complete removal of such uncertainties should not be realistic, particularly in routine isotope measurements of a great number of samples. Here, we review the principles of stable isotope analysis on the traditional off-line Dual- Inlet and continuous-flow EA/IRMS methods, and also show an applicable calibration and standardization sequence. We hope that this paper is useful for routine application of EA/IRMS technique to various studies in geochemistry, ecology, biology, food science, and other area of sciences. 1. D/H 13 / N/ 14 N 1990 O2 N2 Dual Inlet IRMS Wada and Hattori, 1976; DeNiro and Epstein, 1978, 1980; Minagawa et al., / EA/IRMS IRMS continuous-flow Preston and Owens, 1983; Fry et al., 1992; Brenna et * arbon and Nitrogen stable isotope analysis by EA/IRMS ** SI Rie Sato: SI Science O., LTD Hongo, Sugito-Machi, Kitakatsushika-Gun, Saitama, , Japan *** Yaeko Suzuki: Japan ertification Services, Inc higasaki-higashi, Tsuzuki, Yokohama, Kanagawa, , Japan orresponding author. Rie Sato r-sato@shoko.co.jp Tel: ; Fax:

2 al., 1997; Brand, He Bong and Lee, 1997; Olsen et al., 2006 EA/IRMS EA/IRMS EA/IRMS Ohlsson and Wallmark, 1999; Schmitt et al., 2003;, 2008; Ogawa et al., 2010 Dual Inlet EA/IRMS EA/ IRMS 2. δ Table.1 δ δ = [ (R / R ) 1 ] 1000 ( 1) R=H/L H L heavy light 13 / 12, 15 N/ 14 N 3.DualInlet Dual Inlet 2 continuous-flow Table 2 O2 N2 Table1. Isotope compositions of international standards. Rario, H/L* Value, H/L* H % L % Vienna Standard Mean Ocean Water(VSMOW) 2 H/ 1 H Vienna PeeDee Belemnite (VPDB) Air (AIR) 17 O/ 16 O O/ 16 O / O/ 16 O O/ 16 O N/ 14 N * H and L indicate heavy and light isotope components, respectivery. Ratio Values are taken from Fry (2006). Table2. omparison of Dual Inlet and EA/IRMS Dual Inlet EA/IRMS Target Element Size Precision apacity ( ) Preparation Measurement day 15 min Gas N 1-3 mmol H week 20 min 1-5 μmol 10 min N Bulk 1 day O 1-10 μmol 15 min H 5-50 μmol

Rario, H/L* Value, H/L* H % L % Vienna Standard Mean Ocean Water(VSMOW) 2 H/ 1 H 0.00015576 0.015574 99.984426 Vienna PeeDee Belemnite (VPDB) Air (AIR) 17 O/ 16 O 0.0003799 0.0379 99.

3 / EA/IRMS Pyrex tube for gas collection Ag uo Sample u min 850 2h Quartz tube ryogenic trap Hg Toepler pump Vacuuming and sealing in quartz tube ombustion of organic matter to N 2, O 2, H 2 O ryogenic purification of N 2 and O 2 by using vacuum line Fig.1. Schematic of Dual Inlet method for carbon and nitrogen isotope analysis. Fig.1, Sato et al. Fig min 850 2h O2 N2 H2O Dual Inlet O2 196 H2O / 72 N2 PDB PDB IAEA Table 3 Oztech Table3. International references and their δ 13 and δ 15 N values. Isotope ratio( ) Name Abbreviation δd VSMOW δ 18 O VSMOW δ 13 VPDB δ 15 N AIR Inaternational standard(from IAEA and NIST) VSMOW Water 0 0 SLAP2 Water GISP Water Benzoic Acid IAEA Benzoic Acid IAEA Polyethylene IAEA-H ellulose IAEA-H Sucrose (ANU) IAEA-H TS-Limestone NBS Ammonium Sulfate IAEA-N Ammonium Sulfate IAEA-N Porassium Nitrate IAEA-NO Other reference materials(from Indiana Univ.) Acetanilide # Acetanilide # Acetanilide # Urea # Urea # Urea # Benzoic acid #A Benzoic acid #B Other reference materials(from SI science) L-Alanine Histidine Glycine L-Alanine N enriched

International references and their δ 13 and δ 15 N values.

4 4.EA/IRMS 4.1. EA/IRMS Fig. 2 Fig. 3 EA/IRMS EA onflo IRMS EA/IRMS P EA Ox % He % 1800 r2o3 O2 NOX H2O o3o4/ag NOX Red N2 H2O Mg(lO4)2 O2 N2 G onflo IRMS onflo % O2 N2 IRMS N2 O2 He O2 He onflo IRMS Ion Source 3 N2 m/z m/z = 14 N 14 N ( 2) 29 = 14 N 15 N + 15 N 14 N ( 3) 4 15 N/ 14 N 29/28 = 2 ( 15 N/ 14 N) ( 4) m/z 30 NO O2 m/z = O 16 O ( 5) 45 = O 16 O O 16 O O 17 O ( 6) 46 = O 16 O O 17 O O 17 O O 16 O O 18 O ( 7) /44 = 13 / ( 17 O/ 16 O) ( 8) 46/44 = 2 ( 13 / 12 )( 17 O/ 16 O) + ( 17 O/ 16 O) ( 18 O/ 16 O) ( 9) O/ 16 O 18 O/ 16 O 10 raig, 1957; Santrock et al., 1985 He Sample O 2 Quartz wool r 2O 3 Quartz wool o 3O 4/Ag Quartz wool Oxidation furnace Reduction furnace Auto sampler Quartz wool uo Quartz wool u Quartz wool uo Quartz wool EA Water trap Mg(lO 4) 2 G olumn He He Ref. O 2 Ref. N 2 Magnet Detector Ion Source onflo IRMS m/z 28 or 44 Intensity (V) 29/28 or 45/44 Reference O 2 Reference N Sample O 2 2 Sample N2 Time (s) Jump to O 2 mode with He dilution Fig2. Schematic of EA/IRMS system. Fig.2, Sato et al. Fig3. Representative chromatogram of EA/IRMS. Fig.3, Sato et al. 24

45 46 5 6 7 44 = 12 16 O 16 O ( 5) 45 = 13 16 O 16 O + 12 17 O 16 O + 12 16 O 17 O ( 6) 46 = 13 17 O 16 O + 13 16 O 17 O + 12 17 O 17 O + 12 18 O 16 O + 12 16 O 18 O ( 7) 8 9 45/44 = 13 / 12 + 2 ( 17

5 / EA/IRMS 17 O/ 16 O = ( 18 O/ 16 O) ( 10) 13 / O/ 16 O EA/IRMS P δ δ 4.3 δ 18 O 4.2. EA/IRMS mg 30 μg 1.0 mg 80μg Fig. 4 m/z mv m/z mv m/z mv m/z mv 5 9 mm 4.3. P δ δ EA/IRMS Dual Inlet He onflo IRMS IRMS (a) arbon (b) Nitrogen δ 13 ( vs VPDB) δ 15 N ( vs Air) m/z 44 Intensity (V) m/z 28 Intensity (V) Fig.4. Relationship between sample amount and determined d values: (a) carbon and (b) nitrogen. The marked area indicates the actual value with an error of Fig.4, Sato et al.

0 δ 13 ( vs VPDB) -19.4-19.6-19.8 δ 15 N ( vs Air) 2.5 2.0 1.5-20.0 0 5 10 15 20 25 30 35 40 1.

6 δ δ EA/IRMS Air VPDB Table 4 Sequence-1 δ 3 δ δ δ 1 δ EA/IRMS Table 4 Sequence-2 δ 3 δ δ P δ 3 δ δ δ / δ 1.0 δ He He O2 He Fig. 5 Table4. Sequences for δ 13 and δ 15 N analysis Sequence-1 Sequence-2 Working standard A A for stability check A A Working standard A A for calibration B B Sample Working standard A A B Sample

δ δ δ / δ 1.0 δ 10 15 1 3 4.4. He He O2 He Fig. 5 Table4.

7 / EA/IRMS 4.5. EA/IRMS δ 13 ( vs VPDB) m/z 44 Intensity (V) Fig5. Relationship between He dilution pressure and determined δ 13 value. Fig Method 5. Suzuki et al., 2008; Nakashita et al., ; Anderson and Smith, Fig. 7 (a) arbon (b) Nitrogen Fig.5, Sato et al. δ 13 ( vs VPDB) δ 15 N ( vs Air) Sample Num. Sample Num. Fig.6. Precision and memory effects on the replicate analyses for (a) δ 13 and (b) δ 15 N. 27 Fig.6, Sato et al.

, 2008; Nakashita et al., 2008 2006; Anderson and Smith, 2006 2009 Fig. 7 (a) arbon (b) Nitrogen Fig.5, Sato et al.

8 AOA 11 4sugar 7% 4sugar = (δ 13 p δ 13 H ) /(δ 13 P (-9.7) ) 100 ( 11) AOA Fig g 4 ml 2 ml Na2WO2 H2O 2 ml mol/l rpm Jonathan W. White, sugar 12% 4sugar 7% δ 13 p = δ 13 H = δ 15 N ( vs Air) New Zealand Australia Japan δ 13 ( vs VPDB) 4 sugar (%) δ 13 ( vs VPDB) Fig7. δ 13 - δ 15 N plot of beef samples. Sugar % Fig8. δ 13 of 4 sugar-contaminated honey. Fig. 28 Fig.7, Sato et al.

White, 1989 4 4sugar 12% 4sugar 7% δ 13 p = δ 13 H = δ 15 N ( vs Air) New Zealand Australia Japan δ 13 (

9 / EA/IRMS Anderson K. A. and Smith B. W. (2006) Effect of season and variety on the differentiation of geographic growing origin of pistachios by stable isotope profiling. J. Agric. Food hem. 54, Bong Y. and Lee. K. (2007) A fast, simple calibration method for organic carbon isotope analysis using continuous-flow elemental analyzer interfaced with an isotope ratio mass apectrometer. Anal. Sci. 23, Brand W. A. (1998) Isotope ratio mass spectrometry: Precision from transient signals. In: Karjalainen E. J., Hesso A. E. and Karjalainen U. P. (Eds.), Advance in Mass Spectrometry 14, Elsevier Science Publishers B.V., pp Brenna J. T., orso T.N., Tobias H. J. and aimi R. J. (1997) High-precision continuous-flow isotope ratio mass spectrometry. Mass Spectrum. Rev. 16, , DeNiro M. J. and Epstein S. (1978) Influence of diet on the distribution of carbon isotopes in animals. Geochim. osmochim. Acta 42, DeNiro M. J. and Epstein S. (1980) Influence of diet on the distribution of nitrogen isotopes in animals. Geochim. osmochim. Acta 45, Fry B. (2006) Stable Isotope Ecology, Springer Science+Business Media, LL. Fry B, Brand W., Mersch F. J., Tholke K. and Garritt R. (1992) Automated analysis system for coupled δ 13 and δ 15 N measurements. Anal. hem. 64, , Minagawa M., Winter D. A. and Kaplan I. R. (1984). omparison of kjeldahl and combustion method for measurement of nitrogen isotope ratio in organic matter. Anal. hem. 56, Matthias S., Iain R., Rolf S. and Markus L. (1998) Oxygen isotope analysis of cellulose: An interlaboratory comparison. Anal. hem. 70, Nakashita R., Suzuki Y., Akamatsu F., Iizumi Y., Korenaga T. and hikaraishi Y. (2008) Stable carbon, nitrogen, and oxygen isotope analysis as a potential tool for verifying geographical origin of beef. Anal. him. Acta 617, δ 15 N, No.5 Ogawa N. O., Nagata T., Kitazato H. and Ohkouchi N. (2010) Ultra sensitive elemental analyzer/isotope ratio mass spectrometer for stable nitrogen and carbon isotope analyses. In: Ohkouchi N., Tayasu I. and Koba K. (Eds.), Earth, Life and Isotopes, Kyoto University Press, in press. Ohlsson K. E. A. and Wallmark P. H. (1999) Novel calibration with correction for drift and non-linear response for continuous flow isotope ratio mass spectrometry applied to the determination of δ 15 N, total nitrogen, δ 13 and total carbon in biological material. Analyst 124, Olsen J. Seierstad I., Vinther B., Johnsen S. and Heinemeier J. (2006) Memory effect in deuterium analysis by continuous flow isotope ratio measurement. Int. J. Mass. Sectrom. 245, Preston T. and Owens N. J. P. (1983) Interfacing an automatic elemental analyser with an isotope ratio mass spectrometer: the potential for fully automated total nitrogen and nitrogen-15 analysis. Analyst 108, Schmitt J., Glaser B. and Zech W. (2003) Amountdependent isotopic fractionation during compoundspecific isotope analysis. Rapid ommun. Mass Spectrom. 17, Suzuki Y., hikaraishi Y., Ogawa N. O., Ohkouchi N. and Korenaga T. (2008) Geographical origin of polished rice based on multiple element and stable isotope analyses. Food hem. 109, Japanese Journal of Ecology 47, Wada E. and Hattori A. (1976) Natural abundance of 15 N in paniculate organic matter in the North Pacific Ocean. Geochim. osmochim. Acta 40, White J. W. (1989) Honey protein as internal standard for stable carbon Isotope ratio detection of adulteration of honey. J. ASSO. Of f. Anal. hem. 72,

(2007) A fast, simple calibration method for organic carbon isotope analysis using continuous-flow elemental analyzer interfaced with an isotope ratio mass apectrometer. Anal. Sci. 23, 1447-1449.

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