• Analytical Science and Technology
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• v.27 no.3
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• pp.140-146
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• 2014

An internal standard was used in PCID (post column isotope dilution) to improve the accuracy and precision in quantification of various chemical species. The error occurring in the column was the largest in HPLC-ICP/MS (high performance liquid chromatography-inductively coupled plasma/mass spectrometry) when PCID and other traditional quantification methods were compared with each other. Internal standard was effective in correcting the loss of sample in the column to improve accuracy and precision. When applied to SeMet, using MeSecys or $Se^{4+}$ as an internal standard, relative errors were reduced from 31% and 13% to less than 1%, while standard deviations were reduced from 5.1% and 6.9% to 1.5% and 0.2%, respectively. Positive aspects of using an internal standard in PCID were compared with other quantitative techniques and discussed in detail.

• Bulletin of the Korean Chemical Society
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• v.35 no.3
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• pp.821-827
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• 2014

An isotope dilution liquid chromatography tandem mass spectrometry (ID LC-MS/MS) method has been developed and applied to the determination of arsenobetaine (AsB, ${(CH_3)_3}^+AsCH_2COO^-$) from oyster candidate certified reference material (CRM). The exact matching isotope dilution approach was adopted for accurate determination of AsB using $^{13}C_2$-labeled AsB as an internal standard. Efficiencies of different AsB extraction methods were evaluated using a codfish reference material and a simple sonication method was selected as the method of choice for the certification of the oyster candidate CRM. The hydrophilic interaction liquid chromatography (HILIC) combined with electrospray ionization tandem mass spectrometry (ESI/MS/MS) in selected reaction monitoring (SRM) mode was optimized for adequate chromatographic retention and robust quantification of AsB from codfish and oyster samples. By analyzing 12 subsamples taken from each 12 bottles systematically selected from the whole oyster CRM batch, the certified value of AsB was determined as $6.60mg{\cdot}kg^{-1}{\pm}0.31mg{\cdot}kg^{-1}$ and it showed excellent between-bottle homogeneity of less than 0.42%, which is represented by relative standard deviation of 12 bottles from the CRM batch. The major source of uncertainty was the certified value of the AsB standard solution.

• Analytical Science and Technology
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• v.17 no.1
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• pp.29-36
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• 2004

An analytical method of polybrominated diphenyl ethers in soil samples by isotope dilution method using gas chromatography/mass spectrometry (GC/MS)-selected ion monitoring (SIM) was described. PBDEs in soil were extracted with soxhlet extractor and then silica and florisil solid phase extraction (SPE) methods as purification of extract were compared. After clean-up, the extractions were analyzed by GC/MS with SIM mode. Quantitation was performed isotope dilution method using four $^{13}C$ isotopically labeled PBDEs as internal standards. This developed method was validated for eight congeners of PBDEs in the concentration range 0.04~4 ng/g in soil and the average recovery of the analytes ranged 30.8~110.8% for florisil and 44.4~110.7% for silica, respectively. The method detection limits of PBDEs were 0.04~0.3 ng/g.

• Analytical Science and Technology
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• v.27 no.6
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• pp.269-276
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• 2014

A short study for the uncertainty of post column isotope dilution method has been performed for the analysis of Selenomethionine in HPLC-ICP/MS. Major error sources studied were concentration and the flow rate of Se isotope solution, atomic weights of Se in spike and sample, and isotope ratio measured for the spiked sample. Uncertainties were obtained for each factor and the contribution for the total concentration uncertainty was 54.4% and 0.61%, 0.0072% and 0.018%, and 45.0%, respectively. The biggest contribution factor was concentration of the spike solution and the second was the isotopic ratio measured for the spiked sample solution. The mass flow rate of spike and atomic weights did not show much contribution. The calculated total uncertainty was $1.46ng{\cdot}g^{-1}$ for the standard SeMet ($126.30ng{\cdot}g^{-1}$). The experimental result was $127.09{\pm}1.46ng{\cdot}g^{-1}$ and the relative uncertainty was 1.20%.

• Mass Spectrometry Letters
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• v.1 no.1
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• pp.29-32
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• 2010

Cross reacting antibodies can cause an overestimation of the results of immunoassays. Therefore, alternative methods are needed for the accurate quantification of steroids. Gas chromatography combined with isotope-dilution mass spectrometry (GC-IDMS) is developed to quantify urinary active androgens, testosterone, epitestosterone and dihydrotestosterone, which are clinically relevant androgens to both hair-loss and prostate diseases. The method devised involves enzymatic hydrolysis with $\beta$-glucuronidase, solid-phase extraction, liquid-liquid extraction using methyl tert-butyl ether and subsequent conversion to pentafluorophenyldimethylsilyl-trimethylsilyl (flophemesyl-TMS) derivatives for sensitive and selective analysis in selected-ion monitoring mode. Flophemesyl-TMS derivatization not only eliminates matrix interference but also has a good peak resolution within a 6 min-run. A selective and sensitive GC technique with flophemesyl-TMS derivatives also allows accurate quantitative analysis of three active androgens when combined with IDMS. The limit of quantification of the three analytes was <50 pg/mL, and extraction recoveries ranged from 91.9 to 102.1%. The precision and accuracy were 1.2~6.5% and 89.0~106.7%, respectively. This GC-IDMS method can be useful for evaluating the drug efficacy and monitoring the biological processes responsible for male-pattern baldness and prostate diseases.

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3228-3232
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• 2010

Malachite green (MG) has been used world-widely in aquaculture as a parasiticide or fungicide. Although MG performed successfully, it has not been permitted for use in aquaculture from European Union, USA, and Canada because of its carcinogenicity and mutagenicity. We developed a sensitive and specific method to determine MG and its principal metabolite, leucomalachite green (LMG), respectively by isotope dilution liquid chromatography mass spectrometry (ID-LC/MS). To enhance the extraction recovery of MG and LMG from fish tissue, an additional step, saponification, was introduced in sample preparation process to remove fat in sample extract, which hampered the performance of SPE columns. The residue of MG and LMG in fish was analyzed using liquid chromatography mass spectrometry in the selected ion monitoring (SIM) mode by monitoring at m/z 329 and 334 for MG and $d_5$-MG and at m/z 331 and 337 for LMG and $^{13}C_6$-LMG, respectively. This method was validated by comparing with the value of the reference material provided by Laboratory Government Chemistry (LGC). The results agreed within the measurement uncertainty and the accuracy was much improved than the provided reference value by LGC.

• Nuclear Engineering and Technology
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• v.45 no.3
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• pp.415-420
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• 2013

A determination method for $^{237}Np$ in spent nuclear fuel samples was developed using an isotope dilution method with $^{239}Np$ as a spike. In this method, inductively coupled plasma mass spectrometry (ICP-MS) was taken for the $^{237}Np$ instead of the previously used alpha spectrometry. $^{237}Np$ and $^{239}Np$ were measured by ICP-MS and gamma spectrometry, respectively. The recovery yield of $^{237}Np$ in synthetic samples was $95.9{\pm}9.7$% (1S, n=4). The $^{237}Np$ contents in the spent fuel samples were 0.15, 0.25, and $1.06{\mu}g/mgU$ and these values were compared with those from ORIGEN-2 code. A fairly good agreement between the measurements (m) and calculations (c) was obtained, giving ratios (m/c) of 0.93, 1.12 and 1.25 for the three PWR spent fuel samples with burnups of 16.7, 19.0, and 55.9 GWd/MtU, respectively.

• Mass Spectrometry Letters
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• v.8 no.3
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• pp.49-52
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• 2017

Ibuprofen is one of the most popular analgesic and antipyretic drugs. An isotope dilution mass spectrometry method based on LC/MS was developed as a candidate reference method for the accurate determination of ibuprofen in pharmaceutical tablets. Isotope labelled ibuprofen, $ibuprofen-d_3$, was added as an internal standard into sample extracts. Ibuprofen and $ibuprofen-d_3$, was analysed by LC/MS in a selected ion monitoring (SIM) mode to detect ions at m/z 205 and 208, respectively. The repeatability and reproducibility of the developed ID-LC/MS method were tested for the validation and assessment of metrological quality of the method.

• Bulletin of the Korean Chemical Society
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• v.22 no.2
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• pp.205-209
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• 2001

Uniformly-doped silicon thin films were fabricated by ion beam sputter deposition. The thin films had four levels of copper dopant concentration ranging between 1 ${\times}$1019 and 1 ${\times}$ 1021 atoms/cm3 . Concentrations of Copper dopants were determined by the isotope dilution inductively coupled plasma mass spectrometry (ICP-MS) to provide certified reference data for the quantitative surface analysis by secondary ion mass spectrometry (SIMS). The copper-doped thin films were dissolved in a mixture of 1 M HF and 3 M HNO3 spiked with appropriate amounts of 65 Cu. For an accurate isotope ratio determination, both the detector dead time and the mass discrimination were appropriately corrected and isobaric interference from SiAr molecular ions was avoided by a careful sample pretreatment. An analyte recovery efficiency was obtained for the Cu spiked samples to evaluate accuracy of the method. Uncertainty of the determined copper concentrations, estimated following the EURACHEM Guide, was less than 4%, and detection limit of this method was 5.58 ${\times}$ 1016 atoms/cm3.

• The Journal of the Petrological Society of Korea
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• v.10 no.3
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• pp.190-201
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• 2001

Isotope Dilution Mass Spectrometry(IDMS) is one of the analytical method which uses enriched isotope spikes and analyzes the abundance of element by comparison of the spectrum between spiked mass and non-spike mass. Especially, the Thermal Ion Mass Spectrometry with isotope dilution technique (in general ID-TIMS) is the most accurate method of the chemical analysis, which enables us to obtain the data better than 1% in accuracy and precision. In IDMS, enriched isotope spike is one of the most important factor in order to obtain the best data. For rare earth elements, in general, a mixture of /sup 138/La, /sup 142/Ce, /sup 145/Nd, /sup 149/Sm, /sup 151/Sm, /sup 151/Eu, /sup 157/Gd, /sup 163/Dy, /sup 167/Er, /sup 171/Yb, and /sup 176/Lu is used as composite spike. IDMS is very useful in geochronology and REE geochemistry. Especially, it is very effective in studying the “tetrad effect” of rare earth elements in natural samples.