Simultaneous determination of the (2)h/(1)h, (17)o/(16)o, and (18)o/(16)o isotope abundance ratios in water by means of laser spectrometry

We demonstrate the first successful application of infrared laser spectrometry to the accurate, simultaneous determination of the relative (2)H/(1)H, (17)O/(16)O, and (18)O/(16)O isotope abundance ratios in water. The method uses a narrow line width color center laser to record the direct absorption spectrum of low-pressure gas-phase water samples (presently 10 μL of liquid) in the 3-μm spectral region. It thus avoids the laborious chemical preparations of the sample that are required in the case of the conventional isotope ratio mass spectrometer measurement. The precision of the spectroscopic technique is shown to be 0.7‰ for δ(2)H and 0.5‰ for δ(17)O and δ(18)O (δ represents the relative deviation of a sample's isotope abundance ratio with respect to that of a calibration material), while the calibrated accuracy amounts to about 3 and 1‰, respectively, for water with an isotopic composition in the range of the Standard Light Antarctic Precipitation and Vienna Standard Mean Ocean Water international standards.     

A gas chromatographic separation for the h and C stable isotope ratio determination of coal compounds

A new, completely automated gas chromatography technique has been developed to separate the different gaseous compounds produced during underground coal gasification for their (13)C/(12)C and D/H isotope ratio measurements. The technique was designed for separation and collection of H(2), CO, CO(2), H(2)O, H(2)S, CH(4), and heavier hydrocarbons. These gaseous compounds are perfectly separated by the gas-phase chromatograph and quantitatively sent to seven combustion and collection lines. H(2), CO, CH(4), and heavier hydrocarbons are quantitatively oxidized to CO(2) and/or H(2)O. The isotopic analyses are performed by the sealed-tube method. The zinc method is used for reduction of both water and H(2)S to hydrogen for D/H analysis. Including all preparation steps, the reproducibility of isotope abundance values, for a quantity higher than or equal to 0.1 mL of individual components in a mixture (5 mL of gases being initially injected in the gas chromatograph), is ±0.1‰ for δ(13)C(PDB) and ±6‰ for δD(SMOW).     

Measuring methane and its isotopes 12CH4, 13CH4, and CH3D on the surface of Mars with in situ laser spectroscopy

In light of the recent discovery of methane on Mars and its possible biological origin, a strategy is described for making in situ measurements of methane and its isotopes on the surface of Mars by laser spectroscopy in the 3.3-microm wavelength region. An instrument of reasonable mass (approximately 1 lb) and power (few watts) is capable of measuring mixing ratios down to 0.1 part per 10(9) by volume, a hundred times lower than recently reported observations. Making accurate measurements of 13CH4 and CH3D will be more difficult. For measuring delta13C to 10/1000 and deltaD to 50/1000, sample preconcentration will be required to approximately 3 parts per 10(6) by volume for delta13C and to approximately 40 parts per 10(6) by volume for deltaD. This need would be mitigated by the discovery of larger local abundances of methane near the source regions.     

Conversion of O(2) into CO(2) for High-Precision Oxygen Isotope Measurements

An improved procedure of (18)O/(16)O ratio measurements by means of oxygen conversion to CO(2) is developed, which allows one to obtain the true δ(18)O values with a precision of ±0.05‰ in oxygen samples down to 7 μmol. The isotopic exchange between quartz glass and oxygen gas was measured in the temperature range of 600-900 °C, and it was found to be less than 0.2%.     

Detection of synthetic testosterone use by novel comprehensive two-dimensional gas chromatography combustion-isotope ratio mass spectrometry

We report the first demonstration of comprehensive two-dimensional gas chromatography combustion-isotope ratio mass spectrometry (GC×GCC-IRMS) for the analysis of urinary steroids to detect illicit synthetic testosterone use, of interest in sport doping. GC coupled to IRMS (GCC-IRMS) is currently used to measure the carbon isotope ratios (CIRs, δ(13)C) of urinary steroids in antidoping efforts; however, extensive cleanup of urine extracts is required prior to analysis to enable baseline separation of target steroids. With its greater separation capabilities, GC×GC has the potential to reduce sample preparation requirements and enable CIR analysis of minimally processed urine extracts. Challenges addressed include online reactors with minimized dimensions to retain narrow peak shapes, baseline separation of peaks in some cases, and reconstruction of isotopic information from sliced steroid chromatographic peaks. Difficulties remaining include long-term robustness of online reactors and urine matrix effects that preclude baseline separation and isotopic analysis of low-concentration and trace components. In this work, steroids were extracted, acetylated, and analyzed using a refined, home-built GC×GCC-IRMS system. 11-Hydroxyandrosterone and 11-ketoetiocolanolone were chosen as endogenous reference compounds because of their satisfactory signal intensity, and their CIR was compared to target compounds androsterone and etiocholanolone. Separately, a GC×GC-quadrupole MS system was used to measure testosterone (T)/epitestosterone (EpiT) concentration ratios. Urinary extracts of urine pooled from professional athletes and urine from one individual that received testosterone gel (T-gel) and one individual that received testosterone injections (T-shots) were analyzed. The average precisions of δ(13)C and Δδ(13)C measurements were SD(δ(13)C) approximately ±1‰ (n = 11). The T-shot sample resulted in a positive for T use with a T/EpiT ratio of >9 and CIR measurements of Δδ(13)C > 5‰, both fulfilling World Anti-Doping Agency criteria. These data show for the first time that synthetic steroid use is detectable by GC×GCC-IRMS without the need for extensive urine cleanup.     

Precise and traceable (13)C/(12)C isotope amount ratios by multicollector ICPMS

A new method for the measurement of SI traceable carbon isotope amount ratios using a multicollector inductively coupled mass spectrometer (MC-ICPMS) is reported for the first time. Carbon (13)C/(12)C isotope amount ratios have been measured for four reference materials with carbon isotope amount ratios ranging from 0.010659 (delta(13)C(VPDB) = -46.6 per thousand) to 0.011601 (delta(13)C(VPDB) = +37 per thousand). Internal normalization by measuring boron (11)B/(10)B isotope amount ratios has been used to correct for the effects of instrumental mass bias. Absolute (13)C/(12)C ratios have been measured and corrected for instrumental mass bias and full uncertainty budgets have been calculated using the Kragten approach. Corrected (13)C/(12)C ratios for NIST RM8545 (Lithium Carbonate LSVEC), NIST RM8573 (L-Glutamic Acid USGS40), NIST RM8542 (IAEA-CH6 Sucrose) and NIST RM8574 (L-Glutamic Acid USGS41) differed from reference values by 0.06-0.20%. Excellent linear correlation (R = 0.9997) was obtained between corrected carbon isotope amount ratios and expected carbon isotope amount ratios of the four chosen NIST RMs. The method has proved to be linear within this range (from (13)C/(12)C = 0.010659 to (13)C/(12)C =0.011601), and therefore, it is suitable for the measurement of carbon isotope amount ratios within the natural range of variation of organic carbon compounds, carbonates, elemental carbon, carbon monoxide, and carbon dioxide. In addition, a CO2 gas sample previously characterized in-house by conventional dual inlet isotope ratio mass spectrometry has been analyzed and excellent agreement has been found between the carbon isotope amount ratio value measured by MC-ICPMS and the IRMS measurements. Absolute values for carbon isotope amount ratios traceable to the SI are given for each NIST RM, and the combined uncertainty budget (including instrumental error and each parameter contributing to Russell expression for mass bias correction) has been found to be < 0.1% for the four materials. The advantage of the method versus conventional gas source isotope ratio mass spectrometry measurements is that carbon isotope amount ratios are measured as C(+) instead of CO2(+), and therefore, an oxygen (17)O correction due to the presence of (12)C(17)O(16)O(+) is not required. Organic compounds in solution can be measured without previous derivatization, combustion steps, or both, thus making the process simple. The novel methodology opens new avenues for the measurement of absolute carbon isotope amount ratios in a wide range of samples.     

Diode laser absorption measurements of CH(3)Cl and CH(4) near 1.65 microm

Two distributed-feedback (InGaAsP) diode lasers were used to record high-resolution absorption spectra of the parallel and the perpendicular components of the 2nu(4) band of methyl chloride (CH(3)Cl) and the 2nu(3) band of methane (CH(4)) near 1.65 mum. The room-temperature absorption measurements, which were conducted in a multipass cell with a variable path length (878-1020 cm), were used to determine the mole fractions of the constituent gases and thus demonstrate species-specific, nonintrusive concentration measurements of species with overlapping spectra.     

High-precision continuous-flow measurement of delta13C and deltaD of atmospheric CH4

We describe our development of a CH4 preconcentration system for use with continuous-flow gas chromatograph combustion isotope ratio mass spectrometry (GC/C/IRMS). Precision of measurement of delta13C-CH4 is 0.05/1000 (1sigma) on multiple 60-mL aliquots of the same ambient air sample. The same front-end on-line CH4 preconcentration system allows us to measure deltaD of CH4 by gas chromatography IRMS when the combustion furnace is replaced with a pyrolysis oven (GC/P/IRMS). Precision of measurement for deltaD-CH4 is 1.5/1000 (1sigma) using 120 mL of ambient air based on multiple aliquots of the same air sample. These are the first reported measurements of atmospheric CH4 using GC/P/IRMS methodology. Each isotope analysis can be made much more rapidly (30-40 min) than they could using off-line combustion of an air sample (1-6 h) followed by conventional dual-inlet IRMS measurements (12-20 min), while requiring much less total volume and retaining a comparable level of precision and accuracy. To illustrate the capabilities of our preconcentration GC/C/IRMS system, we compare the results of measurement of 24 background air samples made using both GC/C/IRMS and conventional vacuum line/dual-inlet IRMS methodology. The air samples were collected on a shipboard air sampling transect made across the Pacific Ocean in July 2000 and are part of an ongoing atmospheric CH4 research program. The average difference between the two methods of IRMS analyses on these 24 samples is 0.01 +/- 0.03/1000 (95% confidence interval) for delta3C-CH4. These are the first measurements to be reported of air samples directly intercompared for delta13C-CH4 using both GC/C/IRMS and dual-inlet IRMS measurement methodology. Measurement of deltaD-CH4 of these air samples is also presented as an illustration of the ability of this system to resolve small isotopic differences in remote air. High-precision measurement of delta13C and deltaD of atmospheric CH4 made using our coupled preconcentration GC/IRMS system will greatly improve our ability to utilize isotopic data in understanding spatial and temporal changes in atmospheric CH4 and the biogeochemistry of its sources and sinks.     

Use of laser spectroscopy to measure the 13C/12C and 18O/16O compositions of carbonate minerals

The stable carbon and oxygen isotope compositions of carbonate minerals are utilized throughout the earth and environmental sciences for various purposes. Here, we demonstrate the first application of a prototype instrument, based on off-axis integrated cavity output laser spectroscopy, to measure the carbon and oxygen isotope composition of CO(2) gas evolved from the acidification of carbonate minerals. The carbon and oxygen isotope ratios were recorded from absorption spectra of (12)C(16)O(16)O, (13)C(16)O(16)O, and (12)C(16)O(18)O in the near-infrared wavelength region. The instrument was calibrated using CaCO(3) minerals with known δ(13)C(VPDB) and δ(18)O(VSMOW) values, which had been previously calibrated by isotope ratio mass spectrometry relative to the international isotopic standards NBS 18 and NBS 19. Individual analyses are demonstrated to have internal precision (1 SE) of better than 0.15‰ for δ(13)C and 0.6‰ for δ(18)O. Analysis of four carbonate standards of known isotopic composition over 2 months, determined using the original instrumental calibration, indicates that analyses are accurate to better than 0.5‰ for both δ(13)C and δ(18)O without application of standard-sample-standard corrections.     

Global atmospheric methane: budget, changes and dangers

A factor of 2.5 increase in the global abundance of atmospheric methane (CH(4)) since 1750 contributes 0.5 Wm(-2) to total direct radiative forcing by long-lived greenhouse gases (2.77 Wm(-2) in 2009), while its role in atmospheric chemistry adds another approximately 0.2 Wm(-2) of indirect forcing. Since CH(4) has a relatively short lifetime and it is very close to a steady state, reductions in its emissions would quickly benefit climate. Sensible emission mitigation strategies require quantitative understanding of CH(4)'s budget of emissions and sinks. Atmospheric observations of CH(4) abundance and its rate of increase, combined with an estimate of the CH(4) lifetime, constrain total global CH(4) emissions to between 500 and 600 Tg CH(4) yr(-1). While total global emissions are constrained reasonably well, estimates of emissions by source sector vary by up to a factor of 2. Current observation networks are suitable to constrain emissions at large scales (e.g. global) but not at the regional to national scales necessary to verify emission reductions under emissions trading schemes. Improved constraints on the global CH(4) budget and its break down of emissions by source sector and country will come from an enhanced observation network for CH(4) abundance and its isotopic composition (δ(13)C, δD(D=(2)H) and δ(14)C). Isotopic measurements are a valuable tool in distinguishing among various sources that contribute emissions to an air parcel, once fractionation by loss processes is accounted for. Isotopic measurements are especially useful at regional scales where signals are larger. Reducing emissions from many anthropogenic source sectors is cost-effective, but these gains may be cancelled, in part, by increasing emissions related to economic development in many parts of the world. An observation network that can quantitatively assess these changing emissions, both positive and negative, is required, especially in the context of emissions trading schemes.     

Deployment of a carbon isotope ratiometer for the monitoring of CO2 sequestration leakage

In an effort to monitor leakage from underground CO(2) storage, a field-deployable analyzer capable of rapidly measuring the CO(2) mixing ratio and δ(13)C values (±0.05 ppm(v) ± 0.2‰, 60 s) was deployed to distinguish between biogenic and fossil CO(2) sources. The analyzer was interfaced with a multiport inlet unit to allow autonomous sampling from multiple locations. The instrument and inlet interface were deployed at the Zero Emissions Research and Technology (ZERT) site (Bozeman, Montana, July 14-22, 2009) during a controlled, subsurface release of CO(2) depleted in (13)C. A biogenic diurnal cycle was observed far from the release, and the associated Keeling plot suggested a CO(2) source (δ(13)C = -27.0 ± 0.5‰) consistent with local C(3) vegetation. Inlets near the leak showed large CO(2) mixing ratios (388/>40?000 ppm(v)) whose predominant source was the release CO(2) (inferred δ(13)C = -58.2 ± 0.7‰). Measurements 3 m from the source showed diurnal CO(2) cycles (382-2400 ppm(v)) influenced by leaked CO(2), possibly due to diel air mixing. Finally, the data from all of the sampling inlets was combined to spatially localize the leak position.     

Scope and Mechanistic Study of the Coupling Reaction of α, β-Unsaturated Carbonyl Compounds with Alkenes: Uncovering Electronic Effects on Alkene Insertion vs Oxidative Coupling Pathways

The cationic ruthenium-hydride complex [(C(6)H(6))(PCy(3))(CO)RuH](+)BF(4) (-) (1) was found to be a highly effective catalyst for the intermolecular conjugate addition of simple alkenes to α,β-unsaturated carbonyl compounds to give (Z)-selective tetrasubstituted olefin products. The analogous coupling reaction of cinnamides with electron-deficient olefins led to the oxidative coupling of two olefinic C-H bonds in forming (E)-selective diene products. The intramolecular version of the coupling reaction efficiently produced indene and bicyclic fulvene derivatives. The empirical rate law for the coupling reaction of ethyl cinnamate with propene was determined as: rate = k[1](1)[propene](0)[cinnamate](-1). A negligible deuterium kinetic isotope effect (k(H)/k(D) = 1.1±0.1) was measured from both (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) and (E)-C(6)H(5)CD=C(CH(3))CONHCH(3) with styrene. In contrast, a significant normal isotope effect (k(H)/k(D) = 1.7±0.1) was observed from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene and styrene-d(10). A pronounced carbon isotope effect was measured from the coupling reaction of (E)-C(6)H(5)CH=CHCO(2)Et with propene ((13)C(recovered)/(13)C(virgin) at C(β) = 1.019(6)), while a negligible carbon isotope effect ((13)C(recovered)/(13)C(virgin) at C(β) = 0.999(4)) was obtained from the reaction of (E)-C(6)H(5)CH=C(CH(3))CONHCH(3) with styrene. Hammett plots from the correlation of para-substituted p-X-C(6)H(4)CH=CHCO(2)Et (X = OCH(3), CH(3), H, F, Cl, CO(2)Me, CF(3)) with propene and from the treatment of (E)-C(6)H(5)CH=CHCO(2)Et with a series of para-substituted styrenes p-Y-C(6)H(4)CH=CH(2) (Y = OCH(3), CH(3), H, F, Cl, CF(3)) gave the positive slopes for both cases (ρ = +1.1±0.1 and +1.5±0.1, respectively). Eyring analysis of the coupling reaction led to the thermodynamic parameters, Δ H(?) = 20±2 kcal mol(-1) and S(?) = -42±5 e.u. Two separate mechanistic pathways for the coupling reaction have been proposed on the basis of these kinetic and spectroscopic studies.     

Measurements of (12)CH4 nu4 band halfwidths using a tunable diode laser system and a Fourier transform spectrometer

Air-broadened and N2-broadened halfwidths at room temperature for twenty-five transitions in the 4 fundamental band of '2CH4 have been determined from IR absorption spectra recorded with a tunable diode laser spectrometer. Two tunable diode lasers operating in the 1250-1380-cm(-1) region were used to obtain these data. Air-broadened halfwidths for twenty of these lines were also determined from additional spectra recorded at 0.01-cm(-1) resolution with the Fourier transform spectrometer in the McMath solar telescope complex on Kitt Peak. The air-broadened halfwidths obtained from these two techniques are very consistent with agreement better than 3% in most cases.     

Isotope (18)O/(16)O Ratio Measurements of Water Vapor by use of Photoacoustic Spectroscopy

We applied a photoacoustic spectroscopy technique to isotope ratio measurements of (16)O and (18)O in water-vapor samples, using a pulsed tunable dye laser pumped by a Nd:YAG laser. The fourth overtone bands (4nu(OH)) of water molecules near 720 nm were investigated. We identified the absorption lines of H(2)(16)O and H(2)(18)O in the photoacoustic spectra that we measured by using an (18)O-enriched water sample and the HITRAN database. We measured the difference in the (18)O/(16)O isotope ratios for normal distilled water and Antarctic ice, using the photoacoustic method. The value obtained for the difference between the two samples is delta(18)O = -32 ? 16 per thousand, where the indicated deviation was a 1varsigma value among 240-s measurements, whereas the value measured with a conventional isotope mass spectrometer was delta(18)O = -28 ? 2 per thousand. This method is demonstrated to have the potential of a transportable system for in situ and quick measurements of the H(2)(18)O/H(2)(16)O ratio in the environment.     

Airborne laser infrared absorption spectrometer (ALIAS-II) for in situ atmospheric measurements of N2O, CH4, CO, HCl, and NO2 from balloon or remotely piloted aircraft platforms

The Airborne Laser Infrared Absorption Spectrometer II (ALIAS-II) is a lightweight, high-resolution (0.0003-cm(-1)), scanning, mid-infrared absorption spectrometer based on cooled (80 K) lead-salt tunable diode laser sources. It is designed to make in situ measurements in the lower and middle stratosphere on either a balloon platform or high-altitude remotely piloted aircraft. Chemical species that can be measured precisely include long-lived tracers N(2)O and CH(4), the shorter-lived tracer CO, and chemically active species HCl and NO(2). Advances in electronic instrumentation developed for ALIAS-I, with the experience of more than 250 flights on board NASA's ER-2 aircraft, have been implemented in ALIAS-II. The two-channel spectrometer features an open cradle, multipass absorption cell to ensure minimal contamination from inlet and surfaces. Time resolution of the instrument is 相似文献   

Fast chemical sensor for eddy-correlation measurements of methane emissions from rice paddy fields

A high-frequency-modulation spectrometer with a lead-salt diode laser operating in the nu(4) band of CH(4) at 7.8 mum was used as a fast chemical sensor to measure ambient methane concentrations of 2 ppmv (parts in 10(6) volume-mixing ratio) with a time resolution of 10 Hz for micrometeorological flux measurements. To assess the quality of the data on methane emissions from rice paddy fields, we compared eddy-correlation measurements with simultaneously recorded emission data from the state-of-the-art closed-chamber technique and showed that the closed-chamber measurements were 60%-90% higher than were the eddy-correlation measurements during the campaign. This outcome demonstrates that diode-laser spectroscopy is a valuable tool for quality assurance.     

High-precision measurement of variations in calcium isotope ratios in urine by multiple collector inductively coupled plasma mass spectrometry

We describe a new chemical separation method to isolate Ca from other matrix elements in biological samples, developed with the long-term goal of making high-precision measurement of natural stable Ca isotope variations a clinically applicable tool to assess bone mineral balance. A new two-column procedure utilizing HBr achieves the purity required to accurately and precisely measure two Ca isotope ratios ((44)Ca/(42)Ca and (44)Ca/(43)Ca) on a Neptune multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS) in urine. Purification requirements for Sr, Ti, and K (Ca/Sr > 10?000; Ca/Ti > 10?000?000; and Ca/K > 10) were determined by addition of these elements to Ca standards of known isotopic composition. Accuracy was determined by (1) comparing Ca isotope results for samples and standards to published data obtained using thermal ionization mass spectrometry (TIMS), (2) adding a Ca standard of known isotopic composition to a urine sample purified of Ca, and (3) analyzing mixtures of urine samples and standards in varying proportions. The accuracy and precision of δ(44/42)Ca measurements of purified samples containing 25 μg of Ca can be determined with typical errors less than ±0.2‰ (2σ).     

Application of antimonide lasers for gas sensing in the 3-4-microm range

Antimonide semiconductor laser devices designed for continuous-wave emission in the 3-4-mum spectral range have been investigated with respect to spectroscopic applications. Representative data on the mode structure, output power, noise characteristics, far-field pattern, and modulation response are presented. Selected laser devices have been applied for methane (CH(4)) and formaldehyde (HCHO) measurements by use of a high-frequency modulated diode laser spectrometer. From an Allan variance analysis of experimental data a detection limit for HCHO of 120 pptv (where 1 pptv = 10(-12) volume mixing ratio) with a 40-s integration time and for CH(4) of 2 ppbv (where 1 ppbv = 10(-9) volume mixing ratio) with 20-s integration time were determined. The results show that, for selected gases, InAsSb lasers can be an alternative to lead-salt diode lasers.     

Real-time diode laser measurements of vapor-phase benzene

An absorption spectrometer equipped with a IV-VI semiconductor tunable mid-IR diode laser was used to make sensitive measurements of benzene (C(6)H(6)) gas in the 5.1-microm spectral range. Wavelength modulation coupled with second-harmonic detection achieved accurate real-time quantification of benzene concentrations down to a minimum detection limit of 1 ppmv with an integration time of 4 s. A variety of calibrated benzene-sensing measurements were made, including the determination of the benzene concentrations in vehicle exhaust and headspace vapors from unleaded gasoline and other liquids. Kinetic phenomena, including the monitoring of benzene evaporation and absorption/desorption by granulated activated carbon were observed with the instrument. Measurements were performed that allowed experimental determination of the activation energy for desorption of benzene from activated carbon, which was found to be 198 meV/molecule (19.0 kJ/mol).     

pH-Dependent Equilibrium Isotope Fractionation Associated with the Compound Specific Nitrogen and Carbon Isotope Analysis of Substituted Anilines by SPME-GC/IRMS

Solid-phase microextraction (SPME) coupled to gas chromatography/isotope ratio mass spectrometry (GC/IRMS) was used to elucidate the effects of N-atom protonation on the analysis of N and C isotope signatures of selected aromatic amines. Precise and accurate isotope ratios were measured using polydimethylsiloxane/divinylbenzene (PDMS/DVB) as the SPME fiber material at solution pH-values that exceeded the pK(a) of the substituted aniline's conjugate acid by two pH-units. Deviations of δ(15)N and δ(13)C-values from reference measurements by elemental analyzer IRMS were small (<0.9‰) and within the typical uncertainties of isotope ratio measurements by SPME-GC/IRMS. Under these conditions, the detection limits for accurate isotope ratio measurements were between 0.64 and 2.1 mg L(-1) for δ(15)N and between 0.13 and 0.54 mg L(-1) for δ(13)C, respectively. Substantial inverse N isotope fractionation was observed by SPME-GC/IRMS as the fraction of protonated species increased with decreasing pH leading to deviations of -20‰ while the corresponding δ(13)C-values were largely invariant. From isotope ratio analysis at different solution pHs and theoretical calculations by density functional theory, we derived equilibrium isotope effects, EIEs, pertinent to aromatic amine protonation of 0.980 and 1.001 for N and C, respectively, which were very similar for all compounds investigated. Our work shows that N-atom protonation can compromise accurate compound-specific N isotope analysis of aromatic amines.