• Economic and Environmental Geology
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• v.54 no.1
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• pp.151-160
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• 2021

2:1 clay minerals such as smectite incorporating ammonium were extracted to investigate the ammonium behavior and nitrogen isotope characteristics for two different sediment cores which were collected from shimmering sites on seafloor of the Wakamiko crater, southwestern Japan. Inorganic nitrogen contents in clay fraction were estimated by calibration curve based on consistently decreasing carbon and nitrogen ratio during the treatment to decompose organic materials, after removing inorganic carbon. The results show that the proportions of inorganic nitrogen for total nitrogen in clay fraction of SWS site(Core#1094MR: av. 18.2%) are higher than those in SES site(Core#1093MG: av. 11.5%). Relatively good crystallinity of the former suggests that exchangeable ammonium was transformed to non-exchangeable ammonium during more evolving diagenetic process. Nitrogen isotope variance of clay fraction(SES site: Core#1093MG: -4.4 ~ +0.2 ‰, av. -2.4 ‰; SWS site: Core#1094MR: -0.7 ~ +3.0 ‰, av. +1.5 ‰) during sequential decomposition of exchangeable ammonium suggests that heat flow derived from deep magma led to nitrogen isotope fractionation between dissolved ammonium and ammonia in the fluids involved in the formation of 2:1 clay mineral incorporating ammonium with local temperature variation.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.18 no.1
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• pp.47-52
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• 2013

Despite the usefulness of nitrogen isotope tracer experiments in nitrogen cycling studies, there are not such many measurement data mainly due to the difficulties in analytical methods. Although Gardner et al. (1996) developed a relatively simple and accurate method that can measure ammonium isotope using HPLC and used it widely in various N dynamics studies, the technique was not adopted to other laboratories. An HPLC-RTS system using updated HPLC pumps that can perform the same measurements as that of Gardner et al. (1996) was built. The result of standard sample showed linear increase of RTS with the $^{15}N$ proportions. Centroid retention times calculated with Matlab$^{(R)}$ program enhanced the linearity of the response. In a sea water incubation experiment spiked with $^{15}NH_4{^+}$, the uptake and regeneration of ammonium could be separately estimated using the temporal change of $^{15}N/^{14}N$.

• Mass Spectrometry Letters
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• v.8 no.3
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• pp.59-64
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• 2017

In clinical diagnosis, it's well known that the abnormal level of uric acid (UA) in human body is implicated in diverse human diseases, for instance, chronic heart failure, gouty arthritis, diabetes, and so on. As a primary method, an isotope dilution mass spectrometry (IDMS) has been used to obtain the accurate quantity of UA in blood or serum and also develop the certificated reference material (CRM) so as to provide a SI-traceability to clinical laboratories. Due to the low solubility of UA in water, an ammonium hydroxide ($NH_4OH$) has been considered as a promising solvent to increase the solubility of UA that enables the preparation of both UA and its isotope standard solution for next IDMS-based absolute quantification. But, because of using this $NH_4OH$ solvent, it gives rise to the unwanted degradation of UA. In this study, we sought to optimize condition for the stability of UA in $NH_4OH$ solution by varying the mole ratios of UA to $NH_4OH$, followed by ID-LC-MRM analysis. In addition, we also inspected minutely the effect of the storage temperatures. Additionally, we also performed the quantitative analysis of UA in the KRISS serum certificated reference material (CRM, 111-01-02A) with diverse mixing ratios of UA to $NH_4OH$ and then compared those values to its certification value. Based on our experiments, adjusting the mole ratio of 1/2 ($UA/NH_4OH$) with the storage temperature of $-20^{\circ}C$ is an effective way to secure both the solubility and stability of UA in $NH_4OH$ solution for next IDMS-based quantification of UA in serum.

• Mass Spectrometry Letters
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• v.5 no.2
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• pp.52-56
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• 2014

Glycated hemoglobin (HbA1c) is used as an index of mean glycemia over prolonged periods. This study describes an optimization of enzyme digestion conditions for quantification of non-glycated hemoglobin (HbA0) and HbA1c as diagnostic markers of diabetes mellitus. Both HbA0 and HbA1c were quantitatively determined followed by enzyme digestion using isotope dilution liquid chromatography-tandem mass spectrometry (ID-LC-MS/MS) with synthesized N-terminal hexapeptides as standards and synthesized isotope labeled hexapeptides as internal standards. Prior to quantification, each peptide was additionally quantified by amino acid composition analysis using ID-LC-MS/MS via acid hydrolysis. Each parameter was considered strictly as a means to improve digestion efficiency and repeatability. Digestion of hemoglobin was optimized when using 100 mM ammonium acetate (pH 4.2) and a Glu-C-to-HbA1c ratio of 1:50 at $37^{\circ}C$ for 20 h. Quantification was satisfactorily reproducible with a 2.6% relative standard deviation. These conditions were recommended for a primary reference method of HbA1c quantification and for the certification of HbA1c reference material.

• Journal of Environmental Science International
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• v.17 no.5
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• pp.509-516
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• 2008

New functional surfactant, N,N-dimethyl-N-dodecyl-N-(2-methyl benzimidazoyl) ammonium chloride(DDBAC) having benzimidazole(BI) functional group have been synthesized and the critical micellar concentration of DDBAC measured by surface tentiometry and electric conductivity method was $8.9{\times}10^{-4}M$. Micellar effects in DDBAC functional surfactant solution on the hydrolysis of p-nitrophenylacetate(p-NPA), p-nitro-phenylpropionate(p-NPP) and p-nitrophenylvalerate(p-NPV) were observed with change of various pH (Tris-buffer). The pseudo first rate constants of hydrolysis of p-NPA, p-NPP and p-NPV in optimum concentration of DDBAC solution increase to about 160, 280 and 600 times, respectively, as compared with those of aqueous solution at pH 8.00(Tris-buffer). It is considered that benzimidazole functional moiety accelerates the reaction rates of hydrolysis because they act as nucleophile or general base. In optimum concentration of DDBAC solution, the rate constants of hydrolysis of p-NPP and p-NPV increase to about 1.5 and 3.0 times, respectively, as compared with that of p-NPA. It means that the more the carbon numbers of alkyl group of substrates, the larger the binding constants between DDBAC micelle and substrates are. To know the hydrolysis mechanism of p-NPCE(p-NPA, p-NPP and p-NPV), the deuterium kinetic isotope effects were measured in $D_2O$ solutions. Consequently the pseudo first order rate constant ratios in $H_2O$ and $D_2O$ solution, $k_{H_2O}/k_{D_2O}$, were about $2.8{\sim}3.0$ range. It means that the mechanism of hydrolysis were proceeded by nucleophile and general base attack in approximately same value.

• Analytical Science and Technology
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• v.11 no.4
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• pp.231-234
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• 1998

Separation factor for $^6Li$ and $^7Li$ has been determined using ion exchange resin having 1,7,13-trioxa-4,10,16-triazacyclooctadecane ($N_3O_3$) as an anchor group. The ion exchange capacity of the $N_3O_3$ ion exchanger was 2.0 meq/g dry resin. The lighter isotope, $^6Li$, is concentrated in the fluid phase, while the heavier isotope, $^7Li$, is enriched in the resin phase. By column chromatography [0.3 cm(I.D)${\times}$30 cm (height)] using 3.0 M ammonium chloride solution as an eluent, single separation factor, ${\alpha}$, 1.018, i.e. $(^7Li/^6Li)_{resin}/(^7Li/^6Li)_{fluid}$ was obtained by the Glueckauf theory from the elution curve and isotope ratios.

• Analytical Science and Technology
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• v.10 no.6
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• pp.403-407
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• 1997

Separation factor for $^6Li$ and $^7Li$ have been determined using ion exchange resin having 1,7,13-trioxa-4,10,16-triazacyclooctadecane($N_3O_3$) as an anchor group. The lighter isotope, $^6Li$ is concentrated in the solution phase, while the heavior isotope, $^7Li$ is enriched in the resin phase. By Ccolumnl chromatography[0.9cm(I.D)${\times}$20cm(height)] using 2.0M ammonium chloride solution as an eluent, single separation factor, ${\alpha}$, 1.009. i.e.$(^7Li/^6Li)_{resin}$/$(^7Li/^6Li)_{solution}$ was obtained by the Glueckauf theory from the elution curve and isotope ratios.

• Analytical Science and Technology
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• v.31 no.6
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• pp.225-231
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• 2018

Benzoic acid, methyl paraben, and butyl paraben are preservatives that have been used in pharmaceutical, cosmetic, and food products. However, as their toxicities for human have been reported, many nations and organizations including Korea have established a regulation limit for thier usage of these preservatives in food products. The present study developed the isotope dilution liquid chromatography mass spectrometry method for accurate determination of three target preseratives in soysauce. In this study, the isotope dilution liquid chromatography mass spectrometry method was developed for accurate determination of three target preservatives in soy sauce. LC separation was optimized considering the pKa of benzoic acid which is lower than those of methyl and butyl parabens. A C18 column was used with 5 mM ammonium acetate and methanol as mobile phases. Mass spectrometry was operated in negative mode and selected reaction monitoring mode (SRM). Soy sauce sample was cleaned-up with C18 SPE cartridge for removing matrix inferences and color material. Optimized conditions and the method were validated with soy sauce reference materials for the analysis of food preservatives from Health Science Authority in Singapore. The measured values of benzoic acid, methyl and butyl paraben agreed well with reference values within their uncertainties.

• Analytical Science and Technology
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• v.13 no.3
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• pp.297-303
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• 2000

Isotope-dilution inductively coupled plasma mass spectrometry was used to determine trace amounts of Cd, Cu, Pb, Ni and Zn in sediment. Sediment samples were dissolved by microwave digestion with addition of mixed acid ($HNO_3$, HF and $HClO_4$). Lead was determined after separation of alkaline and alkaline earth metals by an ammonium pyrrolidenedithiocarbarmate (APDC) solvent extraction. The other elements were determined after separation of iron, tin and titanium by hydroxide precipitation. Recovery efficiency of the analyte elements was not satisfactory, but most of matrix elements causing the isobaric interference could be effectively eliminated by the separation. Good agreement was achieved with the certified values in the analysis of the two sediment reference materials.

• Korean Journal of Ecology and Environment
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• v.50 no.4
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• pp.452-458
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• 2017

The nitrogen isotope value in both ammonium and nitrate ion were determined at 9 stations during both June and August 2016, in order to understand the origin of DIN at the Han river. ${\delta}^{15}N-NO_3$ and ${\delta}^{15}N-NH_4$ values in 8 stations (CP, SB, MHC, P4, SJ, SBC, P2, SC) were no significant variation. However ${\delta}^{15}N-NO_3$ and ${\delta}^{15}N-NH_4$ values in KK (Kyeongan stream) showed significant different in comparison with 8 stations, with an apparent increase of nitrogen isotope values. These results indicate that antropogenic nitrogen source influence on KK station. Also the ${\delta}^{13}C$ and ${\delta}^{15}N$ isotope ratio of phytoplankton (Diatom and Cyanobacteria) in KK (Kyeongan stream) showed heavier values, compared to other study stations. These results indicate that nitrogen isotope value in phytoplankton effects by different nitrogen source in study sites. These results suggest that the analysis of stable isotope ratios is a simple but useful tool for the identification of dissolved inorganic nitrogen origin in aquatic environments.