Poster Presentation

Pl1

Development of a highly sensitive and selective microplatechemiluminescence enzyme immunoassay for the determinationof free thyroxine in human serum

Hui Chen1,2, Rui-Bo Li1, Xu Wang3, Jin-Ming Lin1,* , Guang-Sheng Guo2
1

The Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology, Department ofChemistry, Tsinghua University, Beijing 100084, China
2
College of Science, Beijing University of Chemical Technology, Beijing 100029, China
3
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal
University, Jinan 250014, China

Thyroxine (3,5,3',5'-tetraiodothyronine,T4) is an important hormone secreted by
the thyroid gland. More than 99.9% of T4 in blood is bound to carrier proteins,
specially to thyroxine-binding globulin (TBG), and the free fraction of T4 (free T4,
FT4) just accounts for ～0.03%[1]. But the FT4 represents the biologically active
form of this compound. It is believed that FT4 could cross cell membranes andinteract with receptors[2], showing metabolically active and clinically relevant effect.
Therefore, measurement of FT4 is of value in assessing thyroid function.
A microplate chemiluminescence enzyme immunoassay (CLEIA) with highsensitivity, selectivity and reproducibility was developed for the determination of FT4
in human serum. A competitive assay has been utilized with horseradish peroxidase(HRP) labeled thyroxine analog in the chemiluminescence (CL) detection. The CL
signal produced by the emission of photons from luminol was directly proportional tothe amount of analyte. The liner range was 0.45-7.5 ng dL-1 and the detection limit
was 0.09 ng dL-1. Experimental conditions, such as temperature, pH, incubation time,
titration level and other relevant variables upon the CL signal have been examined
and optimized. A coefficient of variance of less than 16% was obtained for intra- andinter-assay precision. The present method has been successfully applied to theanalysis of FT4 in human serum. The positive and negative coincidence ratios are
satisfactory. Good correlations were obtained between the results by the proposed
method and radioimmunoassay (RIA) [3], as well as a Bayer ACS-180SE detection
system.

Reference[1] Ekins R. Clin Lab Med.1993; 13: 599-630.
[2] Bouknight AL. Otolaryngol Clin North Am. 2003; 36: 9-15.
[3] Wilke TJ. Clin Chem. 1982; 28: 2051-2056.
*

Corresponding author. Tel.: +86-010-62792343; Fax: +86-010-62792343.

Pl2
Determination of phthalates in fruit jellies by dispersive solid-phaseextraction coupled with high performance liquid
chromatography-mass spectrometry
Yuwei Ma a, Yuki Hashi b, Feng Ji b, Jin-Ming Linc,*aState Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for
Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, Chinab
Shimadzu Global COE for Application & Technical Development, Shanghai 200052, Chinac
The Key Laboratory of Bioorganic Phosphorus Chemistry `& Chemical Biology, Department ofChemistry, Tsinghua University, Beijing 100084, China

Phthalates (PAEs) are widely used as additives in the manufacture of plastics toincrease the flexibility. PAEs are not chemically bound to plastics and can therefore
be easily released into the environment. Consequently, these compounds are
ubiquitous in environmental matrices such as water and soil. PAEs present inpackaging materials may also be released into foods and beverages. Several animalstudies have suggested that certain phthalates and their metabolites are potentially
toxic to human health due to their endocrine-disruptive effects; therefore, presently
PAEs have become a major public health concern. Fruit jellies are also packaged inplastic and during jelly production, contact between the food and plastic material may
occur at various stages; therefore, fruit jellies may also be contaminated by phthalates.
As fruit jellies are very pupular in children, it’s essential to develop phthalates
analysis method in fruit jellies, and this is what the paper concerned.
In this study, a simple, rapid and sensitive method for the determination of 5 kinds ofphthalates including dimethyl phthalate (DMP), diethyl phthalate (DEP), dipropyl
phthalate (DPP), benzyl butyl phthalate (BBP) and dicyclohexyl phthalate (DcHP) in
fruit jellies by liquid chromatography coupled with mass spectrometry has beendeveloped. Samples were pretreated by a dispersive solid-phase extraction method,termed QuEChERS. The standard calibration curves were linear for all the analytes
over the concentration range 10-250 ng ml-1, and the correlation coefficients ranged
from 0.9976 to 0.9991. The limits of detection and limits of quantification were in theranges of 0.09-3.68 ng ml-1 and 0.28-11.25 ng ml-1, respectively. The accuracy of thismethod was evaluated by measuring the recovery from spiked samples. The
recoveries of all five phthalates from samples spiked at three different concentrations(0.01 mg kg-1 , 0.1 mg kg-1, and 1 mg kg-1), were in the ranges of 103%-107%,
95%-102%, and 102%-107%, respectively. The relative standard deviation values(RSDs) for the samples spiked at 0.01mg kg-1, 0.1 mg kg-1 and 1.0 mg kg-1 ranged
from 2.0%-7.6%, 0.3%-2.2%, and 0.5%-1.2%, respectively. The method has beenused for the analysis of real samples and the results are well.
*

Corresponding author. Tel/Fax: +86-10-62792343. E-mail: jmlin@mail.tsinghua.edu.cn

Pl2Biographical Sketch
Name

Yuwei Ma

Title

Graduate student

Address State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center
for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China
No.18 Shuangqing Road, 100085, Beijing, China
E-mail: mayuwei1985@163.com
Birthday19th August, 1985

Nationality China
Research Major
Yuwei Ma graduated from Dept. of Chemistry, Beijing Normal University, Beijing,
China in 2007. In september of the same year, she was matriculated in ResearchCenter for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing,
China. Now she is in the second year of the postgraduate course. She majors inEnvironmental Analytical Chemistry and Prof. Jin-Ming Lin is her supervisor. In thepast one year, she has worked at the determination of phthalates and estrogens in theenvironment.

Pl3

PosterSensitive Protein Detection Based Magnetic Tunnel Junction Sensors
Yunhua Gao*, Kejia Hu,Wenwen Zhou, Jie Lian and Stone Shi
Technical Institute of Physics and Chemistry, CAS, Beijing, 100190, China
E-mail:yhgao@mail.ipc.ac.cn
Magnetoresistive sensors are robust, highly sensitive, have a high potential for integration, and can be
fabricated in cost-effective silicon processes. In the last few years, biochips based on magnetoresistive
sensors have been used for biomolecular recognition assays. In these assays biological probes areimmobilized on the chip surface and complementary target biomolecules can be detected using a magnetic
label. The detection of magnetic fringing fields of the nanoparticle labels is accomplished by amagnetoresistive sensor. The use of superparamagnetic particles as labels is considered a solution to thebackground-signal problems suffered by optical labeling methods employed in vitro disease marker
identification. Because of its sensitivity, its reliability and its easiness of fabrication, GMR and spin valve
sensors are the most commonly used sensor. In order to increase the sensitivity of this technique, anemerging interest in using magnetic tunnel junctions (MTJ) as magnetoresistive sensors is arising due to its
higher magnetoresistance and its potential increase in sensitivity.
The highly sensitive MTJ sensors which are an active electromagnetic chip with integrated CMOS andmagnetic device have been studied for highly sensitive immunosensing over a wide range of target
concentrations. The presence or absence of a single superparamagnetic bead was successfully detected bydirect measurement of fringe fields of beads using MTJ sensors. The real-time detection was also
successfully confirmed by the direct measurement of magnetic fields generated from the superparamagnetic
beads passing an active sensing area of a MTJ sensors integrated with a microfluidic channel. Furthermore,
we proposed the optimization of the magnetoimmuno assay for the highly sensitive and specific detectionof carcinoembryonic antigen (CEA), a diagnostic marker for tumour. Finally, a dose-response curve wasestablished that shows that our MTJ platform can specifically detect CEA down to 10 pg/mL. The MTJ
sensors can be mass-produced at low cost and can detect superpapamagnetic beads bound to the surface
through specific antibody–antigen interactions, making it a potential platform for new simplified and rapid
point-of-care diagnostic tests.

Pl4
Determination of Inorganic Anions in Ethyl Acetate
by In-line Hollow Fiber Membrane Extraction with Ion Chromatography
Zhenzhen Hu and Yan Zhu*
Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028,
Zhejiang, P. R. China
Ion chromatography is a common method to analyze inorganic anions. In the recent
years, with the rapid advances in ion chromatography, it is no longer a difficult
problem to determine inorganic anions even in some water-miscible solvents such as
methanol, iso-propanol, acetone and N-methylpyrrolidone. However, it is still aconundrum to analyze inorganic anions in organic solvents which are slightly soluble
in water.
In this work, a novel hollow fiber membrane extractor was set up to extract inorganic
anions from ethyl acetate using deionized water. Inorganic anions in slightly solubleorganic solvents can be determined by the in-line hollow fiber membrane extractor
coupled with ion chromatography at first time. The analysis of inorganic anions in
ethyl acetate consisted of three steps: (1) using the in-line hollow fiber membrane
extractor to extract anions with deionized water from ethyl acetate meanwhileeliminate the matrix; (2) concentrating the target analytes using a concentration
column; (3) eluting out the concentrated anions for analysis by ion chromatography.
Different aspects of the extraction procedure such as magnetic stirring speed,
extraction flow rate and extraction time were optimized to achieve high extraction
efficiency and good separation results. Satisfactory linear range (0.01-5 mg/L), limitsof detection (0.001-0.005 mg/L) and good repeatability (0.35-7.63 %) were obtained.
The procedure was applied to analyze inorganic anions in two commercial ethyl
acetate samples.

PI 52009 China-Japan-Korea Symposium on Analytical Chemistry
Submission form

Estimation of Emission and Analysis of PCDD/DFs, PCBs andEmerging POPs from Waste Incineration Facilities.
Gon Ok1),2), Seok-hyung Lee1),2), No-jin Park1),2), Sung-min Hwang1),2), Chul-su Kim1)
1) Graduate School of Earth Environmental Engineering, Pukyong National University

2) Dioxin Research Center, Pukyong National University
Summary
In Korea, the levels of PCDD/DFs from the exhaust gas produced from residential, industrial
waste incineration facilities are strictly controlled. However, the control for the Persistent
Organic Pollutants other than PCDD/DFs, such as PCBs, PBDEs, and PCNs do not exist.
Furthermore, the conditions regard to PCBs, PBDEs and PCN exhaustion and their influence
to the environment and human health are not commonly discussed. In this study, the analyticalmethods for the Persistent Organic Pollutants released from the waste incineration facilities
were discussed. Using the analytical methods suggested, the PCDD/DFs, PCBs, PBDEs and
PCNs were analyzed from 30 selected incineration facilities. The size of incineration wasdetermined based on the capacity of waste incinerated in an hour. According to the result, theTEQ-concentration of PCDD/DFs was 0.33ng/m3 for large facility, 1.12 ng/m for medium
facility, and 1.54 ng.m3 for the small facility. The result also showed that the incineration
facilities with stricter emission controls have lower emission concentrations. The
TEQ-concentration of DL-PCBs had the similar pattern to PCDD/DFs. The
TEQ-concentration of DL-PCBs was 0.06 ng.m3 for the small facility, 0.17 ng.m3 for the
medium facility, and the 15.21 ng/m3 for the small facility. In case of PCBs, large incineration
facilities produced lower PCB concentration.
Key word: PCDDs/DFs, DL-PCBs, POPs, PBDEs, PCNs, Incineration facilities, waste
combustion, emission
1. Introduction
Dioxins and dioxin like compounds that are unintentionally produced during the incineration
process are toxic to human health. Such chemicals are toxic, persistent, capable of long-range
transfer and bio-accumulative. The common examples of these chemicals are pesticides,
dioxins and Brominated Flame Retardants. POPs analyzed in this study, such as PCDD/DFs
and DL-PCBs are carcinogenic and known to cause problems in metabolism, reproductive
systems, endocrine systems and the genetic mutation. Internationally, the counter plans forthe elimination of POPs are being requested by UNEP and other organizations. The sources ofthese POPs are usually industries and the waste incineration facilities, where the massive
amounts of chemical solvents are used. Especially the waste incineration facilities are known
to be the important source of PCDD/DFs, PCBs, PCNs and PBDEs. In this study, PCDDs,
PCDFs, DL-PCBs and other new POPs, such as PBDEs and PCNs were monitored, in order toestimate the amount of emission, and to evaluate the overall danger of POPs. Furthermore, theresult of this study will provide the nation wide data for the estimation of POPs emissions
from the waste incineration facilities.
Corresponding author: Gon Ok, 599-1 Daeyeon 3-dong, Namgu, Busan Korea 608-737
gonok@pknu.ac.kr, Professor/Ph.D, Director of Earth Environmental Engineering, Director of Dioxin Research Center2009 China-Japan-Korea Symposium on Analytical Chemistry
Submission form

2. Materials and Methods
2.1 Sample grouping
Each sample was collected based on air pollution process control method. More than 3m3 ofsamples were collected for more than 4 hours. The collected samples were categorized basedon the amount of waste incinerated in an hour. The large waste incineration treated 3ton/hr,
medium incineration treated 0.25 to 3 ton/hr, and the small incinerator treated 0.05 to 0.25
ton/hr. The incineration facilities handle industrial waste, directed waste and medical waste.
However, the majority of wastes treated are the industrial waste. The large incineration
facilities are equipped with exhausted gas absorption systems and the filtration systems, while
the small incineration facilities are furnished with cyclone dust collection system.
2.2 Sample pretreatment
Among the collected exhausted gas sample, the solid samples on the absorbent, such as XAD
were extracted by Soxhlet extraction using 300ml of Toluene for 16 hours. The extractions ofliquid phased samples were processed by liquid-liquid extraction for twice, using 100ml ofToluene.The solvents of the extracted samples were transferred to n-hexane for the clean up.
For the analysis of DL-PCBs, PCNs and PBDEs, multilayer silica gel column (multi silica-gel,
70-230 mesh, neutral, Merck) was used during the clean up process. For the analysis of
PCDD/DFs, both multilayer silica gel column and the alumnia column (activity I, 70-230
mesh, Merck) were used. The instrumental analyses of the samples were completed by High
Resolution Gas Chromatography and Mass Spectrometer (HRGC/HRMS; Agilent GC/
JEOL-800D).
3. Result and Discussion
The recovery rate obtained from the PCDD/DFs, Co-PCBs, PBDEs and PCNs analyticalmethods in this study was over 85% for all the compounds. The total average dioxin
concentration in large incineration facility was 14.6 ng/m3, 44.3 ng/m3 in medium, and107.2ng/m3 in small incineration facilities. The large incineration facilities that have strict
control processes produced low concentration of dioxins, while the smaller facilities produced
higher concentrations of dioxins. The average concentration of total PCBs in large, medium
and small facilities were 191.3 ng/m3, 135.3 ng/m3 and 211.7 ng/m3, respectively.
According to the result, the size of the incineration facility did not cause great impact on theconcentration of total PCB produced. However, since the large incineration facilities produce
more emission, and have longer operation hours compare to the small and medium sizedincineration facilities, the large incineration facilities can make high contribution to the total
nation wide POPs emissions.
Furthermore, in all the facilities, PBDEs and PCNs were also monitored from the emission.
From the result, the need for the process control on Co-PCBs and other dioxin like compound
productions were observed. It could be also concluded that the control of POPs and emerging
POPs sources, and the plans for the POPs eliminations are strongly required in waste
incineration facilities.
Corresponding author: Gon Ok, 599-1 Daeyeon 3-dong, Namgu, Busan Korea 608-737
gonok@pknu.ac.kr, Professor/Ph.D, Director of Earth Environmental Engineering, Director of Dioxin Research Center

Pl6

Application of Polydimethylsiloxane Mini-Disk Extraction to the Analysis ofFloral Aroma by Gas Chromatography and Mass Spectrometry
Hye-Jin Jang, Hyun-Hwa Son, Eun-Ju Cha, Dong-Sun Lee*dslee@swu.ac.kr
Department of Chemistry, Seoul Women’s University 139-774 Korea

This paper reports application of a novel sampling method called headspace
polydimethyl-siloxane (PDMS) mini-disk extraction (HS-PDE) combined with GC/MS
for the analysis of floral aroma from Prunus mume, Lantana camara, and Albizia
julibrissin. The technique uses a prototype PDMS mini-disk (diameter: 8 mm,
thickness: 0.157 mm, weight: 9.4 mg) as a sorption device and very small volume (0.03mL) of acetonitrile as an organic solvent for extraction. The relative extraction
efficiencies of proposed method have been compared with other sampling techniques
based on headspace solid phase micro-extraction (HS-SPME) and mulberry paper bag
micro-solid phase extraction (MPB-m-SPE). This new HS-PDE method is very simple
to use, inexpensive, rapid, requires small sample amounts and solvent consumption.
A①

Diameter : 8mm
Thickness : 0.157 mm (±9.03, RSD%)
Weight : 0.0094 g (±7.33, RSD%)②
Solution A+ Solution B⟲(mixing ratio 10:1)

After 24hr

PDMS disk

Adsorption coating design

Preparation of PDMS disk

B①

Capillary glass tubing(o.d. :0.35mm, length : 6cm)②
PDMS disk③
Injection(1μL)

Solvent (acetonitrile : 30μL)
Shaking(3 sec)
Remove disk

Floral sample

Sand bath(at40℃)

Adsorption

GC/MS

Micro tube (1mL)

Solvent desorption

Column (DB-624)
EI (70eV), ion trap

Fig. Schematic illustration showing how to mold a PDMS disk and headspace PDMS disk extraction.
A, molding method of PDMS disk. B, Procedure of HS-PDE and GC-MS.

P1
Development of New Ultra Violet Photo-Reactor and Its Application to theDetermination of Total Nitrogen and Total Phosphorus
Shuntaro Okauchi and Keiro Higuchi
Kyoritsu Chemical Check Lab., Corp., Ohta-ku, Tokyo 145-0071, Japan
Summary
A new ultra violet photo-reactor was developed to enhance the simplicity, rapidity, safety and low-cost as a
pre-treatment device for the oxidative decomposition method, and was applied to the determination of total
nitrogen and total phosphorus in river water and waste water samples coupled with a simplified measurement
method. The analytical results for practical samples obtained by the proposed reactor showed a good correlation
with those obtained by JIS method.
Key word: Ultra violet photo-reactor, low pressure mercury lamp, total nitrogen and total phosphorus
determination, simplified measurement method
1 Introduction
Kyoritsu Chemical-check Lab., Corp. developed a simplified measurement kits of Pack Test®, which can beused to check the water quality. Pack Test® has been used widely in the practical analysis, because it can behandled easily and quickly, moreover, it is well known to be cost-effective. However, very little pre-treatment
device for a simplified measurement method is available such as distillation, separation, concentration,
decomposition and so on. Therefore, it is desired to develop a new type of pre-treatment device coupled withsimplified measurement method. In this work, an ultra violet photo-reactor was developed for the oxidative
decomposition of organic compounds instead of an autoclave and heating devices, and it was applied to thedetermination of total nitrogen and total phosphorus in the practical water samples by using Pack Test® after thedecomposition.
2 Experimental
The ultra violet photo-reactor consisted of a low pressure mercury lamp (14 mmφ, 13.4 cm length, 4W), twopieces of PTFE tubing (2 mm i.d., 3 mm o.d., 105 cm length) and two sample injection ports. Two pieces ofreaction tubing were wound directly around the mercury lamp. Potassium peroxodisulfate was used as adecomposition reagent. TiO2 was added the sample solution as a photo-catalyst. Two kinds of Pack Test® wereused to detect for nitrate and phosphate, which were based on the Zn reduction - diazotization/coupling andmolybdenum blue spectrophotometric methods. The sample solution of 2 mL was mixed with decomposition
reagent and TiO2 solution before irradiation, and then the mixed solution of 1.5 mL was injected into thereaction tubing by a disposable syringe. The decomposition reaction occurred in the PTFE tubing during
irradiation of ultra violet for 20 min. The resulting nitrate and phosphate in the treated sample solutions wereanalyzed.
3 Result and Discussion
Generally, a quartz coil has been used for the ultra violet irradiation, however, it was reported PTFE tubing
could be also used as a reaction coil in the photo chemical reaction. Therefore, PTFE tubing was selected in thiswork, because of being easy to handle and safely. It was found that TiO2 could be effective to work as a photocatalyst in this photo chemical reaction using the mercury lamp (254 nm) as well as black light (365 nm).
Various practical samples of river and waste water were analyzed by both proposed photo-reactor / Pack Test®
method and autoclave / spectrophotometric method (JIS method). There were good correlations between bothmethods with correlation coefficient of 0.980 (n=70) for total phosphorus
Corresponding author, Shuntaro Okauchi, 5-37-11 Den-enchofu, Ohta-ku,
okauchi-s@kyoritsu-lab.co.jp, Marketing Dept., Kyoritsu Chemical-Check Lab., Corp.

Tokyo

145-0071

Japan,

P2
Determination

of

Total

Arsenic

inEnvironmental

Sampleswith

Decomposition by UV-Irradiation using Hydride Generation Atomic
Absorption Spectrometry
Hideyuki Sakamoto, Akira Yonetani, Kazuyo Miura, Kazuko Yamamoto, Yoshihiro Hirano, Toshihiro Shirasaki
Hitachi High-Technologies Corporation Nanotechnology Products Business Group, Japan
Summary
It is well known that the sensitivity of arsenic measurement by hydride generation atomic absorption
spectrometry (HG-AAS) depends on its chemical form. The measurement of the concentration of total arsenic
often results in considerable errors in a sample containing various arsenic compounds. Therefore, the arsenic
compounds need to be reduced to a homogeneous form. The optimum conditions for ultraviolet irradiation as apretreatment have been investigated in this study. The main aspects examined were reagent concentrations andtime of exposure to ultraviolet radiation. The sample was mixed with K2S2O8 and NaOH, and ultraviolet light
was irradiated using a UV reactor (Model WA-UVR, KYORITSU CHEMICAL-CHECK Lab., Corp.). This
pretreatment method was applied to the analysis of total arsenic in a standard reference material (The Japan
Society for Analytical Chemistry, JSAC0302). Analytical results were in good agreement with the certified
values. The recovery of each of the five arsenic compounds tested (methylarsonic acid, dimethylarsinic acid,trimethylarsine oxide, arsenobetaine and arsenocholine) was about 100%.
Key word:
Arsenic (As), UV irradiation, Hydride generation, Atomic absorption
1 Introduction
The sensitivity of arsenic measurement by hydride generation atomic absorption spectrometry (HG-AAS)
depends on its chemical form. Thus the arsenic compounds present need to be reduced to a homogeneous form
using a microwave digestion system or similar procedure prior to measurement. However, the procedure formicrowave digestion is difficult and time consuming. We tried to use an ultraviolet (UV) irradiation method forthe decomposition of arsenic compounds. The merits of this pretreatment were its ease of use and time-saving
potential. We applied this procedure to the determination of arsenic in environmental samples.
2 Materials and Methods
Five arsenic compounds (methylarsonic acid, dimethylarsinic acid, trimethylarsine oxide, arsenobetaine andarsenocholine) were investigated. Sample solutions containing K2S2O8 and NaOH as oxidation reagents were UV
irradiated for a few minutes using a UV reactor (Model WA-UVR, KYORITSU CHEMICAL-CHECK Lab.,
Corp.). After UV irradiation, the concentration of total arsenic was measured in the sample solutions by hydride
generation atomic absorption spectrometer.
3 Result and Discussion
Organic arsenic compounds were able to be transformed into inorganic arsenic by UV irradiation for a few
minutes. In this study, we decided that the optimal concentration of K2S2O8 was 2% and that of NaOH was 1%.
The total concentration of arsenic in a standard reference material (The Japan Society for Analytical Chemistry,
JSAC0302) and JSAC0302, to which a known concentration of each arsenic compound was added, wasmeasured using this method. Analytical results were in good agreement with the certified values. The recovery ofeach of the five arsenic compounds was about 100%.

P3
Source apportionment of hazardous elements of SPM aerosolin Yokohama, Japan
Md. Firoz Khan1, *, Yuichiro Shirasuna2, Koichiro Hirano2 and Shigeki Masunaga1
1

Yokohama National University, Japan, 2Yokohama City Research Institute for Environmental Science, Japan

Unaccounted

Secondary/refuseburning

Mineralresuspension

Industry

Road traffic

Soil dust

Contribution of sources (mg/m3 )Summary
An extensive chemical analysis of Suspended particulate matter (SPM) mass was conducted to measure metals(Mg, Al, Ca, V, Cr, Mn, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ag, Cd, Cs, Ba, Pb and Bi), water soluble ions (Na+,NH4+, K+, Ca2+, Cl-, NO3- and SO42-) and carbonaceous mass (EC and OC). PCA-APCS technique was employed
to apportion the sources. Automobile was a significant source at urban site and rapidly evolving industries inassociation with secondary aerosol was predominant at sub-urban site. Moreover, many hazardous elements
existed into the sources may bolster the exposure of human health in current locations.
Key words: SPM, aerosol, source apportionment, anthropogenic
1 Introduction
Suspended particulate matter (SPM) is increasingly received attention and broadly accepted as a potent air
pollutant in urban locations and released from wide ranges of sources. SPM triggers respiratory diseases [1, 2].
In addition, SPM causes visibility reduction [3] in urban atmosphere. Thus, it was considered as a mostsignificant pollutant to be routinely monitored in ambient air. However, inadequate studies have been
investigated in apportionment of SPM in Japan [4, 5]. Therefore, particular emphasis was given to be conducting
comprehensive source analysis of hazardous elements in SPM contemplating substantial number of compositions
and several locations in Yokohama, Japan.
2 Materials and Methods
SPM aerosol samples were collected at an urban (Hiranuma) and a sub-urban (Nagahama) site of Yokohama,Japan from April 1999 to May 2005. The SPM samples were subjected to analysis for metals, water soluble ionsand carbonaceous mass using ICP-MS, ion chromatography and CHN analyzer, respectively. Principle
Component Analysis and Absolute Principle Component Score (PCA-APCS) along with Multiple Linear
Regression (MLR) were employed to resolve the contributing sources.
3 Result and Discussion
SPM concentrations were measured as 34.2 mg/m3 and
Urban
12
10
22.9 mg/m3 at urban and sub-urban sites, respectively.
Sub-urban
8
PCA-APCS were appropriately applied and identified
6
4
four distinct sources as shown in Figure 1. Soil dust
3
2
accounted for 3.6 and 4.6 mg/m of SPM mass at urban
0and sub-urban sites. Road traffic contributed significantly
larger at urban (7.2 mg/m3) than at sub-urban (5.7 mg/m3).
Industrial contribution rendered 7.4 and 1.4 mg/m3 at
urban and sub-urban sites. Moreover, mineral
resuspension (6.5 mg/m3) source was predicted at urban
and secondarily formed SPM combining with refuse burning
Fig. 1. Contribution of sources in SPM
3(6.9 mg/m ) was identified at sub-urban site. Unlike sub-urban site, tracers of traffic were profoundly interfering
into SPM pollution at urban site. In contrast, industrial combustion in association with secondarily formed
aerosol mass was greatly contributed at sub-urban site. Major tracer of mineral resuspension being widely used
into cement and other construction materials was found in significant quantities at urban site.
Reference
1. Dockery et al., 1993. An association between air pollution and mortality in six U.S. cities. N. Engl. J. Med. 329, 1753-1759. 2. Pope andDockery, 2006. Health effects of fine particulate air pollution: Lines that connect. J. Air & Waste Manage. Assoc. 56, 709–742. 3. Watson,
2002. Visibility: science and regulation. J. Air Waste Manage Assos. 52: 628-713. 4. Wang et al., 2006. Size distribution and anthropogenic
sources apportionment of airborne trace metals in Kanazawa, Japan. Chemos. 65: 2440-2448. 5. Kawashima et al., 2005. Source
apportionment for PM2.5 in Yokohama city. Abstracts. A. Meeting of the Geo. Soc. Jpn 52, 179.
Corresponding author, Md. Firoz Khan, Graduate School of Environment & Information Sciences, Yokohama National University, 79-7,
Tokiwadai, Hodogaya-ku, Yokohama, 240-8501, Japan. Email:d07tf902@ynu.ac.jp

P4
Examination of VOC Analysis in soil by Direct Head Space-GC/MS
Ryouta KANAI1), Kazutoshi SUGITA1), Kei HIRATA1), Toru MITSUKUNI1), Harumi SHINOZAKI1), Shinya
ITO1), Yoshiaki, IWASAKI1), Sumio GOTO2)
1)
Mitsubishi Chemical Analytech Co.,Ltd., 2) Azabu University
Summary
The prompt method for analyzed VOC in soil was required. We developed the Direct Head Space-GC/MS
method that is very easy and quickly. Initially, soil sample was put into the vial. Next, cap was tightened andinternal standard was added to the sample using micro-syringe. Lastly, the vial with sample set to theauto-sampler for GC/MS. GC/MS system carried out agitation with heating, injection sample gas from head
space of vial and SIM and SCAN measurement. Linearity from 10ng to 500ng was recognized for 23 VOCs
containing benzene. Relative standard division for each compound was less than 10%. These results were similar
to containing test, and reflected to soil pollution.
Key word: Direct Head Space GC/MS, benzene, VOC, soil,
1 Introduction
Recently, soil pollution by harmful compounds was increased in Japan. Ministry of Environmental said numbersof soil survey was increased to 1371 in 2007 from 64 in 1997. The cases of over criteria were 732 cases. These
cases contained heavy metal pollutions, organic solvent contaminations, PCB and DIOXIN contaminations. Soil
Contamination Countermeasures Act had been worked from 2003.
VOC compounds are typical contents of soil pollution. For example, the land around cleaning factory had been
contaminated by cleaning agent containing trichloroethylene and tetrachloroethylene. The countermeasure forsoil pollution is very expensive because the survey of land circumstances, analysis of harmful compound in soil
and land clean-up. Therefore, simple and quick techniques for analysis are needed for cost down and short termof survey. In this study, we developed new VOC analysis technique in soil that called Direct Head Space GC/MS.
2 Materials and Methods
2-1: Preparation of soil contaminated by VOCs.
Black soil was filtrated by 5mm mesh sieve. VOC mixture was spiked to black soil and soil was mixed well.
High and low contaminated soils were prepared.
2-2: Leaching test
Soil sample was put into the glass
F ig .1 Sch e m a tic s o f D H Sbottle. Mineral water was added
G C/M S M e a su re m e n t
A u to m a ti o n
into this bottle without space in thebottle. Sample in the bottle wasstirred gently for four hours. Test
So il Sa m p l eelution sample was prepared after
filtration that sample. VOC
containing in this elution sample
was analyzed by Head Space
GC/MS
GC/MS system.
2-3: VOC concentration in soil
Sp i k e th e IS
VOC was extracted from soil withmethanol for 3 times. After
Kazutoshi SUGITA, Mitsubishi Chemical Analytech Co.,Ltd, 8-5-1, Chuo, Ami-Machi, Inashiki-gun, Ibaraki JAPAN,
6306378@cc.m-kagaku.co.jp

centrifuge, methanol was move to another bottle. Using this methanol sample, VOC was analyzed by Head Space
GC/MS system.
2-4: Head Space GC/MS measurement
Liquid sample was put into the vial and added salts. After cap was tighten, added internal standard. This vial was
hold at 60℃ for 30 minutes. Then, gas from vial was injected to GC/MS.
2-5: Direct Head Space GC/MS measurement
The soil sample is put into the vial. And internal standards were added in this vial. This vial was hold at 60℃ for
30 minutes. Then, gas from vial was injected to GC/MS. Fig.-1 shows the head space GC/MS system.

Response [Area of Native/Area of IS]

3 Result and Discussion
3-1: Dose-Response relationship and accuracy
Initially, linearity of calibration curve and accuracy for thisFig-2 Calibration Curve for Trichloroethylene
method were checked. Four cases of calibration curves were
6
Vial with water 15mL and NaCl 3g
tried. In the case A, this is the normal method, only standard
y = 0.020 x + 0.005
2solution with IS was added after cap was tightened. In the caseR = 1.000
B, influence of water was considered in agitation. In the case of
4
Vial
y = 0.008 x + 0.065
high volatile and high water solubility compounds that like2
R = 1.000
methanol, it was expected that vaporization of those compounds
Vial with water 1mL
y = 0.008 x - 0.038
2
were influence by water contents. Then, water (1mL) was added2
R = 0.999
Vial with soil 3g
in vial initially, and cap was tightened, standard solution with IS
y = 0.008 x - 0.008
2
R = 1.000
was added in the vial at last. In the case C, it was similar0
condition of soil sample. Soil sample without VOCs was added
0
100
200
300
400
500
600
Dose [ng]in vials at first. Standard solution with IS was added in the vial
after cap was tightened. In the case D, this is the same method
for water sample. In the all cases and 23 VOCs, good linearity were recognized at ranged from 10ng to 500ng(Fig.-2).
The lowest standard solutions (10ng) were repeated for 5 times because of accuracy for DHS-GC/MS method
was confirmed. Those results from 4 cases were compared with elution test and containing test. The standard
deviations for these cases were less than 10%.
3-2: Comparison for test method
Soil sample contaminated with VOCs was measured by three Methods (Leaching test, solvent extraction and
DHS-GC/MS) and results were compared. Table shows the results from three methods. The results from
DHS-GC/MS were similar with solvent extraction method. As leaching test, because sample was dilution withwater, results were ten times lower than other methods. Thus, DHS-GC/MS was very useful for VOC analysis in
soil.

Comparison between three analytical methods for VOC in soilnBz
(mg/L)
Leaching Test→HS-GC/MS
2
0.49(mg/kg)Solvent Extraxtion→HD-GC/MS 5
5.1±0.23(mg/kg)
DHS-GC/MS
55.6±0.70

TCE
0.54
5.8±0.28
6.6±0.88

PCE
0.81
9.7±0.95
8.2±1.9

Kazutoshi SUGITA, Mitsubishi Chemical Analytech Co.,Ltd, 8-5-1, Chuo, Ami-Machi, Inashiki-gun, Ibaraki JAPAN,
6306378@cc.m-kagaku.co.jp

P5Development of Continuous Monitoring System for Ammonium ion in
Industrial Waste Brine Water by Using FIA Technique
Keiro Higuchi
Ogawa & Co., Ltd. Kobe 657-0029, Japan
Summary
A Fully automated continuous monitoring system by using conventional flow injection spectrophotometry wasdeveloped, and applied to the determination of ammonium ion in industrial waste brine water. The systemenables one to monitor highly concentrated ammonium ion without any manual dilution procedure. The
chemistry is based on the reaction of ammonium ion with salicylate and hypochlorite to form a coloredindophenol blue derivative. The monitoring of ammonium ion was continuously carried out for 14 days in thedrains in iodine and natural gas manufacturing factories.
Key word: ammonium ion, brine water, continuous monitoring, flow injection spectrophotometry.
1 Introduction
The national effluent standards are uniformly applied in Japan, especially for ammonia, ammonium
compounds, nitrate and nitrite compounds. When the provisional effluent standard is applied, thepermissible limit is regulated to be 100 mg/L as nitrogen, which value means total of N-NH4+ multipliedby 0.4, N-NO2- and N-NO3-. Brine water flowing underground in Chiba area contains natural gas andiodine, which are separated from brine and made into a product. The waste brine water contains highly
concentrated ammonium ion (approximately 200 mg/L N-NH4+). After separating gas and iodine, it isnecessary to monitor the concentration of ammonium ion continuously in industrial waste brine water. In
this work, a fully automated continuous monitoring system was developed by using FIA technique andapplied to the determination of ammonium ion in the practical waste brine water.
2 Experimental
A peristaltic micro pump was used for propelling the reagent solutions instead of double-plunger pump used inconventional FIA. Six-way rotary valve and multi-positions valve were used for sample injection and sample
changing. A detector was consisted of PTFE tubing (2 mmi.d., 3 mmo.d.) flow cell and LED of 660 nm. A
newly designed sampling pot was used to transport a brine sample from a waste drain. A sample solution fromthe sampling pot is introduced into a sample loop on a six-way injection valve after passing through a suction
filter (10 μm). The sampling and analytical conditions can be controlled by a microcomputer installed in a FIA
system. The data processing was also carried out by the same microcomputer.
3 Result and Discussion
The chemistry was based on the reaction of ammonium ion with salicylate and hypochlorite to form a coloredindophenol derivative. In this work, the FIA system and the composition of reagent solutions were changed toreduce the sensitivity to the concentration range of approximately 200 mg/L (N-NH4+) without any manual
dilution procedure. A flow cell and all of flow lines were placed in a temperature - controlled air oven, because
the temperature was changeable at sampling sites. The data obtained is printed out for each analysis, and at least
500 analyses can be stored as electric data. In addition, they can be sent to other computers by e-mail. The
monitoring of ammonium ion was continuously carried out in the practical drains of iodine manufacturing
factories.
Corresponding author, Keiro Higuchi, 3-1-25-501 Hio-cho, Nada-ku, Kobe 657-0029, Japan, khiguchi@river.ocn.ne.jp, FIA
Instruments Div. Ogawa & Co., Ltd.

P6
Flow injection determination of hydrogen peroxide based on fluorescencequenching of chromotropic acid catalyzed with iron(II)Koji Oshita1, Zhen Hai Li2, Yun Hua Gao3, and Shoji Motomizu4
1

Department of International Conservation Studies for Cultural Properties, Faculty of Cultural Properties,
Kibi International University, Japan

2

Analytical and Testing Center of Yanbian University, China

3

Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, China

4

Chemistry and Biochemistry, Graduate School of Natural Science and Technology & Department of Chemistry,
Faculty of Science, Okayama University, Japan
Summary
Flow-injection analysis system (FIA system), which was based on Fe(II)-catalyzed oxidation ofchromotropic acid with hydrogen peroxide, was developed for the determination of hydrogen peroxide. The
chromotropic acid has a fluorescence measured at λem = 440 nm with λex = 235 nm, and the fluorescenceintensity at λem =440 nm quietly decreased in the presence of Fe(II), which was caused by Fe(II)-catalyzed
oxidation of chromotropic acid with hydrogen peroxide. By measuring the difference of its fluorescenceintensity, hydrogen peroxide (1.0 x 10-8 – 1.0 x 10-3 M) could be determined by the proposed FIA system, whose
analytical throughput was 40 samples h-1. The relative standard deviation (RSD) was 1.0% (n = 10) for 4.0 x
10-8 M hydrogen peroxide. The proposed FIA technique could be applied to the determination of hydrogen
peroxide in rain water samples.
Key word: flow-injection analysis, H2O2 determination, Fe(II)-catalyzed oxidation, chromotropic acid
1 Introduction
In the wide field of biochemistry, clinical chemistry, food chemistry, and environmental chemistry,hydrogen peroxide must be simply and sensitively determined in the samples in order to analyze the behavior ofhydrogen peroxide, such as oxidation processes and interaction mechanisms. Therefore, the development of thenovel analytical method for hydrogen peroxide is one of the aims in the analytical science.
2 Materials and Methods
The novel FIA system was developed for the determination of hydrogen peroxide. The hydrogen
peroxide was detected on the florescence quenching of chromotropic acid, which is based on the oxidation
reaction of chromotropic acid with hydrogen peroxide using Fe(II) as a catalyst.
3 Result and Discussion
The chromotropic acid has a fluorescence, which can be measured at λem = 440 nm with λex = 235 nm,
whereas the fluorescence intensity of chromotropic acid at λem = 440 nm is quenched by its oxidation withhydrogen peroxide. The difference of the fluorescence intensity between non-oxidized chromotropic acid (baseline) and oxidized chromotropic acid (signals) provided the negative peaks, which was used as a peak height forthe detection of hydrogen peroxide by the proposed FIA system. It was caused by the oxidation ofchromotropic acid by the hydrogen peroxide. The relative standard deviation (RSD) of ten measurements of 4.0
x 10-8 M hydrogen peroxide was 1.0%, and the limit of detection (LOD) was 5.0 x 10-9 M. The analyticalthroughput was 40 samples h-1.
Corresponding author, Koji Oshita, 8 Iga-machi, Takahashi, Okayama 716-8508, Japan, E-mail Address, oshita@kiui.ac.jp.

P7
Using a Capillary GC Backflush Device for Rapid Analysis-Analysis of Acrylonitrile in ABS Resin Toyohito Wada, Mikiko Asakawa, Takaaki Hiraoka
Shimadzu Corporation Analytical Applications Department, Japan
SummaryThis study reports the results of analyzing acrylonitrile rapidly by backflushing such solvent andhigh-boiling-point contaminants. Shimadzu GC-2010-backflusing system equipped with FID-2010 and
FTD-2010 was used as gas chromatograph. Backflushing after eluting acrylonitrile reduced the analysis time
significantly; including the time for elimination unwanted substances, and analysis time was saved from about 1
hour for normal analysis using GC/FID to 12.4 minutes. For GC/FTD, backflushing N,N-dimethylformamide
allowed rapid, high-sensitivity analysis of acrylonitrile, while simultaneously preventing deterioration of detector
stability. Since using the backflush GC system no need to flush out contaminants for long time at hightemperatures, it can also help to extend the life of columns.
Key word:
Gaschromatography, GC, Backflush, Acrylonitrile, FTD,
Introduction
Testing of materials, such as containers, packaging, cooking implements, or other such items, which has become
an increasing concern in recent years, is analyzed substances with relatively low boiling points. However,extracts from the plastic materials contain large amounts of substances with high boiling points. One example isthe analysis of acrylonitrile, which has attracted attention as a carcinogen and is regulated by the U.S. Food andDrug Administration (FDA) and European Community (EC). It is measured using a flame ionization detector(FID) or flame thermionic detector (FTD), but these analysis require a long time to flush out thehigh-boiling-point substances that come from solvents or plastics. Furthermore, Some solvents have possibility of
causing reduced stability or deterioration of FTD detectors. This study reports the results of analyzing
acrylonitrile rapidly by backflushing such solvent and high-boiling-point contaminants.
Materials and Methods
As gaschromatograph, Shimadzu GC-2010-backflusing system equipped with FID-2010 and FTD-2010 wasused. As Data processing and control of backflushing GC system, Shimadzu GC work station GC-solution wasused.
Result and Discussion
Backflushing after eluting acrylonitrile reduced the analysis time significantly; including the time for elimination
unwanted substances, and analysis time was saved from about 1 hour for normal analysis using GC/FID to 12.4
minutes.
For GC/FTD, backflushing N,N-dimethylformamide allowed rapid, high-sensitivity analysis of acrylonitrile,
while simultaneously preventing deterioration of detector stability.
Since using the backflush GC system no need to flush out contaminants for long time at high temperatures, it canalso help extend the life of columns.

P8
RAPID CHARACTERISATION AND INVESTIGATION OF OIL SHALES BY THERMALDESORPTION-PYROLYSIS-GC/MS USING MULTI-FUNCTIONAL PYROLYZER
Chu Watanabe1), Tetsuro.Yuzawa1), Itsuko Iwai 2), Hans. Luik3)
1) Frontier Laboratories Ltd., R&D, 1-8-14, Saikon, Koriyama, Fukushima, Japan2) Kinryo electro Co., Ltd., Yodogawa-ku, Osaka, Japan
2) Laboratory of Oil Shale and Renewables Research, Tallinn University of Technology, Estonia

Industry burn oil shale directly as a low-grade fuel for power generation and heating purposes and can use
it as a raw material in chemical and construction-materials processing. Oil shale has been gained attention
as a one of the future energy resources as the price of conventional sources of petroleum has risen and as away for some areas to secure independence from external suppliers of energy. However, oil-shale mining
and processing involve a number of environmental issues, such as land use, waste disposal, water use,
waste-water management, especially greenhouse-gas emissions and air pollution. The conventional
analytical methods of oil shales has been used with Fischer Assay and thermogravimetirc analysis but these
are not enough for the fully evaluation of complex composition of oil-shales. In order to minimize theseissues, rapid, reliable and precise analytical methods have been requested for long time.
The analytical system using a vertical type of micro-furnace pyrolyzer combined with capillary column
GC/MS has been demonstrated itself as one of powerful tool for rapid characterization of various artificial
and natural polymers. [1, 2]. In this work, the multi-functional pyrolyzer (Frontier Laboratories; Japan)
was introduced with oil shale sample for the first time to estimate its potential in investigation of the oil
shale organic matter (kerogen) generally known as a natural complex biogeopolymer and ancient precursorof natural petroleum in Earth’s crust. The analytical system consists of pyrolyzer with GC/MS used fortesting of the two representative Estonian Kukersite and Dictyonema oil shales is described as follows.
The system enables both flash pyrolysis and stepwise programmed thermal desorption/pyrolysis using
deactivated stainless steel capillary column (Ultra ALLOY column; Frontier Laboratories Ltd. UA1-30M1.0F), and evolved gas analysis of the oil shales in widely varied temperature region as from 100 to 800 ºC
using simultaneous detection mode of GC/MS and pulse flame photometric detectors (PFPD). As a specificfeature for the Kukersite straight chain aliphatic saturated and unsaturated hydrocarbons with carbon
number up to C17 as well as rare long alkyl chain homologous 5-alkylresorcinols have been displayed in
rapidly generated summary chromatograms. Both flash and programmed pyrolysis express the same
regularities in pyrolysate compound composition while the concentrations of similar compounds differ.
Also, one can see in the chromatograms abundance of aromatic compounds as alkyl derivatives of benzene,
toluene, naphthalene, anthracene and phenanthrene typical not only for Kukersite but for many other oil
shales as well. Furthermore, the trace amount of variety of sulfur compounds were also identified using
PFPD and mass spectrum.
The potential of such multi-functional Py-GC/MS system includes thorough investigation the compounds
formed resulting from Kukersite and Dictyonema flash and programmed pyrolysis, studying the regularities
of formation different compounds depending on pyrolysis temperature creating the fundamentals ofadvanced technologies for oil shale more effective liquefaction in obtaining liquid fuel and chemicals. With
this aim the Estonian Kukersite and Dictyonema oil shales are investigated in the frames of international
collaboration between Frontier Laboratories Ltd. and Laboratory of Oil Shale and Renewables Research at
Tallinn Technical University (Estonia).
1)
2)
3)
4)

C.Watanabe, K.Teraishi, S.Tsuge, H.Ohtani, K.Hashimoto; J. of HRC&CC, Vol14, 269- 272,1991
C.Watanabe, K.Sato,A.Hosaka, H.Ohtani, S.Tsuge; Amer. Lab, 14-15, Oct, 2001
S.Tsuge, etal; Amer.Lab, 35, 32-35, Jan, 2003; 35, 48-52, Mar, 2003
S.Tsuge, H.Ohtani, C.Watanabe; Amer. Lab, 36, 22-26, Feb, 2004.

Keywords: Oils Shales, Kukersite and Dictyonema, Multi-functional pyrolyzer, EGA, Heart-cutting
GC/MS, simultaneous detection with MS and FPD,P9Development of new pyrolysis–GC/MS system incorporated withon-line micro-ultraviolet irradiation for rapid evaluation of photo, thermal,
and oxidative degradation of polymers
Chuichi Watanabe a, Tetsuro Yuzawaa, Shin Tsuge b, Hajime Ohtani ca Frontier Laboratories Ltd., 1-8-14 Saikon, Koriyama, Fukushima 963-8862, Japanb Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japanc Department of Materials Science and Engineering, Graduate School of Engineering, Nagoya
Institute of Technology, Nagoya 466–8555, Japan

Keywords: On-line micro-UV irradiator, Pyrolysis–GC/MS, Evolved gas analysis, Material
degradation, Polymer deterioration

Abstract
A new pyrolysis–GC/MS system incorporating with on-line micro-ultraviolet (UV) irradiation
was developed to make rapid evaluation of the synergistic material deterioration during UV
irradiation (wavelength: 280 - 450 nm) under oxidative atmospheres with appropriate
heating. The basic effectiveness of the system was demonstrated by using polystyrene,
polypropylene and polycarbonate as the test samples. The volatile products evolved during
deterioration of the polymers were analyzed on-line by thermal desorption GC/MS, and thenthe residual degraded polymers were analyzed by evolved gas analysis (EGA)/MS and/or
Py–GC/MS to obtain specific thermograms and pyrograms. Based on these results, thedeterioration mechanism of the polymeric materials during irradiation under oxidative
atmosphere can be evaluated using a polymer sample on the order of sub-milligram within arelatively short period of time.

e-mail address: chu@frontier-lab.com

P10
Control of Concentration of Components and Level of Malodorants in
Kitchen Scraps
Hiroshi SATO1*, Midori Yamamoto1, Toshiyuki HOBO2
1

Faculty of Pharmaceutical Sciences, Nagasaki International University, Huis Ten Bosch, Sasebo, Nagasaki
859-3298, Japan
2
Tokyo Metropolitan University, Minami-Ohsawa, Hachioji, Tokyo 192-0397, Japan
Summary
In this research, two tests were performed to investigate how temperature and oxygen concentration affectthe emission of malodorants as food decays over time. The first test was performed with the focus on temperatureand model of kitchen scraps kept at three temperatures: 5℃, 15℃ and 25℃. The results showed that the model
kept at 25℃ produced the highest concentration of malodorant components; however, there was only a small
difference in the concentration of malodorant components between the models kept at 5℃ and 15℃. The second
test was performed to examine how oxygen concentration affects malodorant emission from food scraps at fiveoxygen concentrations: 0%, 5%, 10%, 15% and 20%. The results showed that the model kept at 5% oxygen
concentration had lower malodorant level; however, after about four days, there was no clear difference inmalodorant level among all the models.
Key words:

kitchen scraps, malodorant, oxygen concentration, putrefaction

1. Introduction
Malodorants are produced from kitchen scraps owing to the growth of microorganisms, which implies thatpreventing such growth would prevent kitchen scraps from emitting malodorants. To examine this idea, we tried
to controle environmental factors, such as temperature, oxygen concentration, carbon dioxide concentration andthe water content of food. The research was conducted focusing on the effects of temperature and oxygen
concentration on malodorant emission.
2. Materials and Methods
Experiment #1:
Models of kitchen scraps were kept at three temperatures: 5℃, 15℃ and 25℃ for 25 days. To measure theconcentration of gases emitted from the models, GC (FPD/FID) and GC/MS were used.
Experiment #2:
The air in the container with the models of kitchen scraps was replaced with a mixture of oxygen andnitrogen with various oxygen concentrations: 0%, 5%, 10%, 15% and 20%. Oxygen concentration was measured
with disposable detectors. Malodorant level was determined by sniffing and GC (TCD) was used to measure theconcentrations of CO2 and CH4 in the container.
3. Results and Discussion
In the first experiment, the results showed that the model kept at 25℃ produced the highest concentrationof malodorant components; however, there was only a small difference in the concentration of malodorantcomponents between the models kept at 5℃ and 15℃. In the second experiment, the model kept at 5% oxygen
concentrations had lower malodorant level; however, after about four days, there was no clear difference inmalodorant level among all the models. Interestingly, the model of kitchen scraps kept at 0% oxygen
concentration showed no change in its appearance after 10 days.
Thus, to prevent malodorant emission from kitchen scraps, it is favorable to keep them in a place at 15℃
and for up to four days, with lower oxygen concentrations.

Corresponding author, Hiroshi SATO, Nagasaki International University, Huis Ten Bosch, Sasebo, Nagasaki 859-3298,
Japan, satoh@niu.ac.jp, Introduction of the author: Dr. Hiroshi Sato received his Master degree in 1983 and received a
PhD degree in Pharmaceutical Sciences (2003) at Kyushu University in Japan. He had worked in Cao corporation during
1985-1987 and then had worked in TOTO LTD during 1987-2006. He is currently an associate professor of Nagasaki
International University. His research is focused on the environmental analysis and bioremediation.

P11

Validation of a Fast Multiresidue Method for theDetermination of Pesticides Residues in Food Using Mini
Solid-Phase Extraction and Large Volume Injection-Gas
Chromatography

R. Sasano, H. Tanizawa
AiSTI SCIENCE CO.,Ltd. / Assort kuroda 2F, 120-6, kuroda wakayama-city wakayama
640-8341, Japan
In recent years, the problem of pesticide residues in food has been raised on a number ofoccasions and concern about the safety of food has increased. In order to respond to theincrease in the number of pesticides subject to inspection according to the adoption of the
Positive List system, the simultaneous analysis of more than 300 constituents is required for
GC/MS (Gas Chromatography/Mass Spectrometry). However, it is difficult to greatly increase
the number of samples inspected, because a pretreatment process of each sample is time
consuming using current analysis techniques. Therefore, in order to accelerate thepretreatment process, we examined fast multiresidue analysis method for the determination ofpesticide residue in food, which combines reducing sample volume using a large volume GC
injection method, and re-concentrating the samples by the solid phase extraction (reversed
phase mode). As a result, conventional procedures, such as liquid-liquid distribution by a1)separatory funnel, and concentration process by an evaporator etc., were able to be omitted.
The pretreatment process time by one person after fractioning was 15 minutes for one sample
and 60 minutes for ten samples.
Moreover, measurement by the SCAN mode is employed because of the difficulty of setting
the ion set etc. in SIM (Selected Ion Monitoring) mode for MS for an increased number ofpesticides to be measured. In each of the food, a 50% or higher recovery rate was obtained formore than 280 constituents of pesticides. Almost all compounds were achieved a relative
standard deviation of ＜10% (n=5).

P12
Validation of a Post-column Reaction GC/FID As an Accurate Assignment
Method of the Specific Values for Organic Compounds
T. Watanabe1,2, K. Kato1, K. Tsunoda2, and T. Maeda1
1National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science andTechnology (AIST), AIST Tsukuba Central 3, 1-1-1, Umezono, Tsukuba, Ibaraki 305-8563, JAPAN
2
Department of Chemistry and Chemical Biology, Gunma University, 1-5-1, Tenjin-cho, Kiryu, Gunma
376-8515, JAPANSummary
For the determination of accurate specific values for organic compounds, an analytical method using post-column
reaction GC/FID system was developed.
The system was equipped with two reactors between achromatographic column and a detector. The separated analytes from the separation column were converted tocarbon dioxide, then, to methane by two reactors, and finally detected by FID as methane. The analyticalmethod was validated with an internal standard addition method and an absolute calibration method using thephthalate esters solution of SI-traceable certified reference material. Obtained results have shown that theanalytical method using the post-column reaction GC/FID system was an accurate assignment method of thespecific value for organic compounds.
Key word: Post-column reaction; GC/FID; reference material; phthalate ester.
1 Introduction
An accurate assignment method of specific values is very important. An analytical method using post-column
reaction GC/FID system was developed for the precise determination of organic compounds more simply andquickly. The system was equipped with two reactors between a chromatographic column and a detector. The
separated analytes from the separation column were converted to carbon dioxide, then, to methane by tworeactors, and finally detected by FID as methane. For showing its effectiveness as an accurate assignment
method, the analytical method was validated with an internal standard addition method and an absolutecalibration method using the phthalate esters solution of SI-traceable certified reference material.
2 Materials and Methods
The certified reference material CERI-jcss-0619 (CRM), eight ester phthalates mixture standard solution, waspurchased from Chemical Evaluation and Research Institute (CERI; Tokyo, Japan). n-Hexane was purchasedfrom Aldrich Chemical Company, Inc. (Milwaukee, WI, USA). n-Eicosane was purchased from Tokyo
Chemical Industry Co., Ltd. (Tokyo, Japan). n-Eicosane was diluted with n-hexane, and this mixture was used
as an internal standard solution.
3 Result and Discussion
The internal standard solution was added to the CRM, and this mixture was measured with the post-column
reaction GC/FID system by an internal standard addition method with n-eicosane as an internal standard.
Obtained values of phthalate esters were compared with the reference values of phthalate esters, respectively.
The obtained values and the reference values were in good agreement with one another. Concentrations of an
unknown phthalate esters mixture was measured with two measurements methods. One of the methods was thepost-column reaction GC/FID system and the other was an absolute calibration method using the CRM. The
results were in good agreement with each other. These results have shown that the analytical method using thepost-column reaction GC/FID system was an accurate assignment method of the specific values for organic
compounds. We will report the design concept for the validation / calibration of standard mixtures.

Corresponding author T. Watanabe at National Metrology Institute of Japan (NMIJ), National Institute of Advanced
Industrial Science and Technology (AIST), AIST Tsukuba Central 3, 1-1-1, Umezono, Tsukuba, Ibaraki 305-8563, Japan.

P13
Determination of Trace Amount of Formaldehyde Based on theSpectrophotometric Measurement of Excess Sulfite for Formation ofFormaldehyde-Sulfite Compound
Yasuyuki Miura and Keita Iuchi
Department of Chemistry, School of Science, Tokai University, Hiratsuka, Kanagawa 259-1292, Japan
Summary
Optimal conditions of reaction of sulfite with formaldehyde and measurement of an excess
sulfite for the reaction were established. A spectrophotometric measurement of an excess
sulfite for formation of sulfite-formaldehyde adduct was carried out by using cobalt (II)-azide
complex reagent. Formaldehyde could be determined from an consumption of sulfite. The
proposed method is successfully applied to determination of t formaldehyde at 10-5 M levels inaqueous solution.
Key word:
Formaldehyde, sulfite, cobalt (II)-azide complex, cobalt (III)-azide complex, spectrophotometry
1 Introduction
We found that sulfite give a catalytic effect on an air-oxidation of cobalt (II) into cobalt (III)in an aqueous solution containing large amounts of azide, in which cobalt (II)-azide complex
indicates purple and cobalt (III)-azide yellow. A spectrophotometric measurement of sulfite at
10-5 M levels based on the catalytic reaction was already investigated and presented.
Otherwise, it is well known that sulfite produce a stable adduct compound via its reaction
with formaldehyde in an aqueous solution. Therefore, if a known amount of sulfite wereallowed to react with formaldehyde to form sulfite-formaldehyde adduct and then a residual
sulfite were measured by the spectrophotometric method using cobalt (II)-azide complex
reagent, determination of formaldehyde can be expected from an consumption of sulfite via its
reaction with formaldehyde.
2 Method
Sample solution (10 ml) containing formaldehyde was mixed with sulfite solution (8 ml) adjusted to pH 6.0 byadding acetate–acetic acid buffer solution (2 ml), and the mixture was allowed to stand for 20 min. A 10.0 ml of
the obtained mixture was added to a reaction solution (pH 5.6) comprised of acetic acid, cobalt (II) chloride andsodium azide and the reaction solution was allowed to stand for 20 min. After diluting it to 25 ml with water,
absorbance of the solution was measured at 370 nm.
3 Result and Discussion
Under the optimal conditions, calibration plots of formaldehyde showed a linear line in therange 0–160 μM with negative slope, because increasing of formaldehyde concentration
caused the decrease of the residual sulfite and also the decrease of absorbance for yellow
cobalt (III)-azide compound, owing to use of a known excess amount of sulfite on the reaction
with formaldehyde. The proposed method can be successfully applicable to determination of
trace amount of formaldehyde in aqueous solution.

P14
Effect of alcohol addition on determination of thiosulfate, sulfite, sulfide
and thiocyanate based on its reaction with cerium(IV) and thefluorescence detection of cerium(III)I. Mikami and Y. Miura
Department of Chemistry, School of Science, Tokai University
Summary
The fluorescence intensity for cerium(III) was extremely increased when thiosulfate, cerium(IV) and ethanol
were coexisted in the reaction solution compared with the case in absence of ethanol. Similar increase offluorescence intensity by addition of ethanol was observed on the determination of sulfite, sulfide andthiocyanate with this method. This method gave much higher sensitivity for the thiosulfate, sulfite, sulfate andthiocyanate measurement compared with a method based on the reaction of cerium(IV) with these reducing
reagents without using methanol.
Key word: fluorescence detection; cerium; thiosulfate; alcohol addition
1 Introduction
An analytical method for the determination of reducing reagents such as thiosulfate, L-ascorbic acid and nitriteusing their reactions with cerium(IV) and the fluorescence detection of cerium(III) has been reported as a
postcolumn fluorescence detection previously [1]. In the determination of thiosulfate by this method, it wasobserved that the intensity of cerium(III) fluorescence was extremely enhanced in the presence of ethanol. In
this work, effect of addition of various alcohols on the determination of thiosulfate and application of this method
to the determination of sulfite, sulfide and thiocyanate have been investigated.
2 Materials and Methods
To a 25 mL of volumetric flask, 18 mL of alcohol aqueous solution, 5 mL of sample solution, 1 mL of
cerium(IV) sulfate - sulfuric acid were added. After dilution with water to a mark of the flask, fluorescenceintensity was measured at regular intervals. Fluorescence of cerium(III) was monitored using excitation andemission wavelengths of 256 nm and 354 nm, respectively.
3 Result and Discussion
To investigate effect of kind of alcohol on the determination of thiosulfate using cerium(III) detection, 2.4
mol/L of various alcohol (methanol, ethanol, 1-propanol and 2-propanol) was added. The fluorescence intensityof cerium(III) for the same concentration of thiosulfate was increased by addition of every alcohol used in thisstudy compared with the case in absence of alcohol. During these alcohol, ethanol exhibited highest increase of
the fluorescence intensity, followed by 1-propanol, methanol, 2-propanol. The fluorescence intensity measured atreaction time for 2 minutes was related to the concentration of thiosulfate. Such enhancement of the fluorescenceintensity by addition of alcohol might be attributed that thiosulfate accelerate reduction rate of cerium(IV) by
alcohol; the reduction rate of cerium(IV) by alcohol is low.
Sulfite, sulfide and thiocyanate instead of thiosulfate were determined on this method with 2.4 mol/L ofethanol addition. Like in the case of determination of thiosulfate, the increase of fluorescence intensity ofcerium(III) by addition of ethanol were observed in the case of determination of sulfite, sulfide and thiocyanate.
[1] Y. Miura, M. Hatakeyama, T. Hoshino, P. R. Haddad, J. Chromatography A, 956 (2002) 77.
Ikko Mikami,1117 Kitakaname, Hiratsuka, Kanagawa 259-1292, Japan, ikmikami@keyaki.cc-u-tokai.ac.jp,
Research interests: FIA, Fluorescence detection, Chemiluminescence detection, Capillary electrophoresis, Analysis of water
quality, Water purification by catalytic methods.

P15
Stationary Phases for Ion Chromatographic Determination of InorganicAnions in Seawater
X.-L. Jiang1, L. Rong2, A. Suzuki1, M. Kobayashi1, L. W. Lim1 and T. Takeuchi1
Gifu University, Japan
2
Xihua University, China
1

Summary
Stationary phases for determination of inorganic anions in seawater have been developed in ion chromatography.
Stationary phases, which allow us to use high-concentration eluents, have been examined in order to avoid effects
of matrix ions contained in seawater. Retention of analyte anions increased with increasing eluent concentration
for poly (ethylene glycol) stationary phases with molecular mass of 10,000 – 20,000, which was advantageous todetermine trace iodide and thiocyanate in seawater samples. Quaternary ammonium surfactants could be directly
introduced onto silica gel via ion exchange followed by hydrophobic interaction. These stationary phases also
allowed us to use high-concentration eluents for determination of nitrate, bromide and nitrate in seawater samples.
Monolithic capillary columns, packed capillary columns and conventional-size columns have been prepared andevaluated. Use of conventional-size columns with 4.6 mm I.D. improved concentration sensitivity and achieved
detection limits at ng/mL levels.

Key word:
Ion chromatography; stationary phases; inorganic anions; seawaterPart of this paper has been published in Bunsekikagaku, 57, 991-999 (2008). Please refer to the paper for thedetails.

Corresponding author: Toyohide Takeuchi, Department of Chemistry, Faculty of Engineering, Gifu University, E-mail:take-t@gifu-u.ac.jp, Professor of Chemistry.

P16
Analysis of Raw Water and Drinking Water by High-throughput Ion
Chromatography
S. Ito, Y. Kobayashi, F. Nakata, S. Satoh and H. Kubota
Tosoh Corporation, 2743-1 Hayakawa, Ayase, Kanagawa 252-1123, Japan
Summary
We present here a technique of ion chromatography analysis which is developed for the high-throughput
measurement of common anions or cations within 5 minutes. The separation was performed with small particle
resin packing, the short column and particular chromatograph system, which are optimized for rapid resolution.
As a result of having applied this method in the analysis of the water samples such as raw water or drinking water,
7 kinds of anions or 6 kinds of cations were separated excellently and measured without any interference.
Key words: Ion chromatography, high-throughput measurement, raw water, drinking water
1 Introduction
Ion chromatography(IC) is an efficient analytical method for determining ionic species in several waters, which
has been used one of the main water quality monitoring method. Recently, the trend of HPLC is high-throughput
and high-pressure analysis. Analysis time of high-throughput HPLC is equal to or less than 3 minutes. On theother hand, in conventional IC analysis, it needs more than 10 minutes for common ionic species analysis. We
developed a high-throughput IC system (IC-2010) and columns (TSK-GEL SuperIC HS series) for analysis timeof less than 5 minutes. In order to realize high-throughput analysis, small particle rigid resin was packed in shortcolumn. And packing method and IC system were optimized for high-pressure analysis. We introduce thesetechniques of system and packing materials in this presentation.
2 Materials and Methods
The chromatographic analyses are performed by ion chromatograph, Tosoh IC-2010 constituted by a dual pump,an on-line degasser, a column oven, an automatic sample injector, a conductmetric detector, a gel-change-able
suppressor module and an auto-dilutor. The data analysis and system control was done by Tosoh IC-WS
processing system. The separation of anions was performed on TSKgel SuperIC-Anion HS (4.6mmI.D. x 10cm)
and TSKguardcolumn SuperIC-A HS (4.6mmI.D. x 1cm) using 3.8mM NaHCO3 + 3.0mM Na2CO3 as eluent.
The separation of cations was performed on TSKgel SuperIC-Cation HS (4.6mmI.D. x 10cm) andTSKguardcolumn SuperIC-C HS (4.6mmI.D. x 1cm) using 3.0mM MSA + 0.4mM 12-crown-6-ether + 0.2mM
histidine as eluent. All the reagents used in this study were guaranteed grade purchased from Wako Pure
Chemical Inc.
3 Result and Discussion
Excellent separation of common anions or cations within 5 minutes was obtained and sensitivity was improved
with this IC system and columns. As the result of having applied this method in the analysis of raw water such as
rain, river water or spring water and drinking water, no interference peaks showed and common ionic species
were measured. Sensitivity and repeatability were satisfied for the measurement of common ionic species in raw
or drinking water. The results showed that this method was useful for the high-throughput measurement ofcommon ions in raw water and drinking water.

Seiji Ito, s_ito@tosoh.co.jp, Tosoh Corporation, 2743-1 Hayakawa Ayase Kanagawa 252-1123, Japan

P17

Simultaneous Determination of Halogen Compounds and
Sulfur Oxides in Flue Gas by Ion Chromatography
Makoto Nonomura
Evaluation Research Institute for Environmental Technology, 2954-1-107, Togasaki,
Misato-shi, Saitama, Japan, 341-0044
Keiko Kurita
Tokyo Metropolitan Industrial Technology Research Institute, Department of Resourceand Environmental Group, 3-13-10, Nishigaoka, Kita-ku, Tokyo, Japan, 115-8586

Ion chromatography (IC) is a suitable analytical method for the determinationof anions. As an analytical method for the halogenated compounds in flue gas,bromine compound, fluorine compound, chlorine and hydrogen chloride (HCl)are listed in JIS. However, IC has not been adopted in JIS except for HCl. It isbecause that these components are absorbed in a 0.1 M sodium hydroxide
solution, it is interfered with the measurement of F- and Cl- ions.
This paper describes the development of the pretreatment equipment for theflue gas analysis by IC, and applied it to real flue gas analysis. The F-,Cl-,Br- andSO42- in the absorbing solution could be clearly separated by IC using
pretreatment equipment. The halogenated compounds and sulfur oxides in fluegas could be simultaneously determined by IC.

P18
Determination of Halogens and Sulfur by Combustion-Ion
chromatography
N.Hayashi1, M.Moriya1,J.Kenmizaki1
1
Mitsubishi Chemical Analytech , Enzo370, Chigasaki, Kanagawa, Japan
SummaryIt’s examination of the total halogen and sulfur analysis using the fully automated combustion- ion
chromatography system. We have a good result, 95-103% recovery on standard sample, fluorite, analysis.
It also can be quick and easy measurement for the sulfur and halogen in organic and inorganic materials.
Key word: Halogen; Combustion; Ion chromatography; Halogen Free;
1. Introduction
Total Halogen and sulfur analysis become important in quality control and monitoring of the environmental
pollution. Therefore, easy method for Halogen and sulfur analysis is required. Combustion is a very superior
method for decomposing Halogen in materials and absorbing it to solution. In addition, ion chromatography is amethod to measure the halogenide ions and sulfate ion in the solutions quickly with high sensitivity. It is very
effective method in many fields for Total Halogen and sulfur analysis in materials that combining two
technologies, combustion and ion chromatography (CIC method). We report it as an introduction of
fully-automated CIC system and measurement examples.
2. Principle
AQF100(Mitsubishi Chemical Analytech
combustion system) is used for combustion.
The sulfur and halogen in samples are reacted tosulfur oxide and hydrogen halogenide by combustion.
The combustion gas is absorbed by absorbent
containing hydrogen peroxide and it is sampled as asulfate ion and a halogenide ion. These ions aremeasured by ion chromatography, and concentrationin sample is determined.

Absorption
Absorption Unit
Unit

Combustion
Combustion Unit
Unit

Wash

Sample Boat

Injection
Valve

O2

Ar/O2

IC
ABC
Drain
Sampling
Absorbent dispenser

H2O

Fig 1 AQF100 combustion system
3. Resulta)Polyethylene standard sample (ERM EC-680K)
1

2

3

Average(ppm)

RSD,%

Recovery,%

Ｃｌ
Ｂｒ

104
96.9

105
95.5

106
97.4

105
96.6

0.95
1

102.6
100.6

Ｓ

73.8

72.8

75.5

74

1.8

97.4

b)Chloride in Glass
1
OPAL Glass
138
Borosilicate
332
Lead Glass
516
Norio hayashi

2
143

3
151

Average(ppm)
144

RSD,%
4.55

Recovery,%
103

330

334

332

0.60

94.9

479

490

495

3.84

99.0

Mitsubishi Chemical Analytech Instruments Division Development group E-mail; n.hayashi@dins.jp

P19
Reference material of sulfur blank solvent for the liquid fuels
Y. Kitamaki1 and K. Kato1
1
Organic Standards Section 1, National Metrology Institute of Japan (NMIJ), AIST, Japan
Summary
The sulfur blank solvent, NMIJ RM 4216-a, for the determination of sulfur in the liquid fuels was developed by
National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology(AIST). Reference value was determined by the combustion followed by the ultraviolet fluorescence method
using the standard addition method. Trap and release unit was used, and the signal appeared without sample
injection was subtracted as the background for the determination of trace sulfur in organic solvent.
Key word: trace sulfur, standard addition method, ultraviolet fluorescence detection, background,reference material, fuel1 Introduction
Sulfur content is one of the important properties to evaluate the quality of the fuel. In petroleum industries,
accurate analysis of sulfur becomes important for the quality control. Moreover, sulfur at sub mg kg-1 to mg kg-1
is well known as the catalyst poison at reformer in fuel cell system. For the determination of low level sulfur,
microcoulometry, X-ray fluorescence method, ion chromatography and ultraviolet fluorescence (UV-FL) method
are common techniques. These methods require calibration standards. In the preparation of sulfur standard
solutions sub mg kg-1 to mg kg-1, high purity sulfur compound or sulfur solution with the higher concentration isdiluted with organic solvents. In this case, sulfur in solvent causes analytical bias. Thus, it is important toestimate the sulfur content in organic solvent. In our poster, it is described the measurement method of the trace
sulfur in organic solvent, and the development procedure of the RM 4216-a.
2 Materials and Methods
Toluene was chosen as the candidate for RM 4216-a. CRM 4215-a was used as the high concentration sulfur
standard solution. A total sulfur analyzer TS-100V (Mitsubishi Chemical Analytech Co., Ltd., Kanagawa, Japan)
was used. For the determination of trace sulfur, a trap and release unit TRU-100 (Mitsubishi Chemical Analytech
Co., Ltd., Kanagawa, Japan) was connected after the combustion tube to accumulate the sulfur dioxide (SO2 )that was formed during combustion of the sample.
3 Results and Discussion
Toluene, the candidate for RM 4216-a was dispensed to 30 mL portion in 350 amber glass ampoules. The
between-bottle homogeneity of RM 4216-a was evaluated by determining 10 amples selected from the lot of 350
amples.
All gravimetric standard addition samples were prepared by spiking RM 4216-a with CRM 4215-a. The 30 mL
alumi-seal vials with mininert valves (GL Sciences Inc., Tokyo, Japan) were used for the preparation of standard
addition samples to avoid the change of concentration due to evaporation of organic solution.
Using the trap and release unit, a signal without sample injection was appeared. It is considered that, when thecondition of the combustion tube temperature is not high enough, impurities containing sulfur in the carrier gases
can not be oxidized to SO2, and no appeared the background signal. Therefore, the signal without sample
injection was subtracted as a background in the determination of trace sulfur in organic solvent using thestandard addition method.

P20
Evaluation of error sources in a gravimetric technique for preparation of areference gas mixture (a case of carbon dioxide in synthetic air)N. Matsumoto1 , T. Shimosaka1 , T. Watanabe1 , K. Kato1
1
National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science andTechnology (AIST), Japan
Summary
Gravimetric blending method is one method of preparing a primary reference gas mixture. The uncertainty of forthe mass measurements is necessary to be equal to or less than a few mg, for preparation of the reference gas
mixtures, under current conditions of our facilities, equipments and materials. There are many sources of errors
in this method. In this study, several sources of errors were re-evaluated on our preparation process of carbon
dioxide in synthetic air. As a consequence of the re-evaluations, it was found that the difference of readings onbalance between reference cylinder and sample cylinder were significant for gravimetric concentrations of thegas mixtures under the certain conditions of our facilities.
Key word: Gas analysis, Gas metrology, Preparation of standard gas, International comparison, Electronicmass comparator
Carbon dioxide (CO2) is one of the most important greenhouse gases. Its concentration in the atmosphere has
been monitored using non-dispersive infrared gas analyzers (ND-IR). High-accuracy and stable reference gas
mixtures in high-pressure gas cylinders are required for the calibration of ND-IR. Measurements of CO2 in theatmosphere require the uncertainty in the concentration of reference gas mixtures be lower than 0.1 mmol/mol.
International comparisons on CO2 in synthetic air at atmospheric level were performed under the direction of theConsultative Committee for the amount of substance (CCQM). Nine national metrology institutes (NMIs)
participated in these comparisons. However, the concentrations of primary gas mixtures (PRMs) by each NMI
were not consistent within 0.1 mmol/mol. The final report of the internal comparison concluded that there areuncertainty factors missing in the uncertainty budget and thus, more work is needed to identify the origins of theobserved discrepancies. In the comparison, all PRMs were prepared using the gravimetric (blending) method.
However, each participant used different equipments, cylinders, gases, method, and, procedures. It is important tofind out the missing error sources.
There are many error sources in this method, as described in annex E of ISO6142:2001. In the gravimetricblending method, the mole fraction of the gas mixture is calculated based on the mass filled into a sample gas
cylinder, the molar mass, and, the composition (the purity and impurities) of parent gases. The mass of eachcomponent gas filled in a sample cylinder is measured as the difference in the masses of the sample cylinder
between before and after the filling of the gas. Accuracy of the mass measurements depends on massmeasurement techniques, gas-filling techniques, and, the quality of the cylinders.
In this presentation, we have re-evaluated the following sources of error;(1)Difference of mass between reference cylinder and sample cylinder (An error on reading of electronic masscomparator), (2) Cooling of a gas cylinder due to the filling of high-purity liquefied CO2, and warming of a gas
cylinder due to filling with dilution gas, (3) Leakage through valve of the high-pressure gas cylinder, (4)Adsorption/desorption of moisture on external cylinder surface, (5) Stable isotope ratio of 13C/12C in CO2 parent
gas, (6) Impurity of the vapor phase in the high-purity liquefied CO2 gas cylinder at various temperatures.
As the result of re-evaluation, it was found that the source (1) was significant [1].
Reference[1] N. Matsumoto, T. Shimosaka, T. Watanabe, K. Kato, Analytical and Bioanalytical Chemistry, 391, 2061-2069(2008).
Corresponding author, Nobuhiro Matsumoto, Tsukuba Central 3, 1-1-1 Umezono, Ibaraki, 305-8563, Japan,
nobu-matsumoto@aist.go.jp, researcher

P21
Study of State of Alkyl Chains for Reversed-Phase: Collapse or Brush up
N. Nagae, K. Yamamoto and C. Kadota
ChromaNik Technologies Inc. 6-3-1 Namiyoke, Minato-ku, Osaka, 552-0001, Japan
Summary
The state of alkyl chains are evaluated by solvation of organic solvent on the stationary phase in reversed-phase
chromatography. Solvation volume of organic solvent in a mixture of organic solvent and water as a mobile
phase to alkyl chain as a stationary phase was measured directly by retention of organic solvent under lower
concentration of organic solvent in a mobile phase, furthermore, indirectly by change of stationary phase volume
obtained from measurement of elution volume of uracil as an non-retained substance under higher concentrationof organic solvent in a mobile phase. THF solvated 6 times more than methanol on the C18 stationary phase,
while acetonitrile solvated 2.5 times. THF solvated in the whole alkyl chain and alkyl chain brushed up whilemethanol solvated on the surface of agglomerating C18 phase.
Introduction
It had commonly been said that ligand collapse made retention decrease under 100% aqueous conditions forreversed-phase liquid chromatography. However Nagae et al. reported at 2000 that reducing retention under
100% aqueous conditions had nothing to do with ligand collapse and its cause was that a mobile phase like water
expelled from the pore of the packing materials by capillarity. In this study, solvation volume of organic solvent
was measured, then the state of alkyl chains was considered.
Materials and Methods
Sunniest C18, Sunniest RP-AQUA (C28) and Sunniest C8 manufactured by ChromaNik Technologies Inc wereused to measure retention time of organic solvents and unraci as a nonretained sample. Methanol, Acetonitrile
and tetrahydrofuran were used as organic solvent.
Result and Discussion
Solvation volume of tetrahydrofuran (THF), acetonitrile andmethanol were measured as shown in Fig.1. THF solvated 6 times
more than methanol on the C18 stationary phase, while acetonitrilesolvated 2.5 times. Solubility of octadecan (C18H38) to not only
water but also methanol is almost zero, so that C18 alkyl chain isconsidered to agglomerate on the surface even if 100% methanol isused as a mobile phase. These results suggested that THF solvated in
the whole alkyl chain and alkyl chain brushed up while methanol
solvated on the surface of agglomerating C18 phase.

P22
Generic Approach to Analysis of Pharmaceutical Salts Including
Inorganic and Organic Counter-ions with Corona CAD
Kyoko Fukushima1, Yasuhiro Kanedai1, Kusuo Hashiguti1, Masaaki Senda1, 2, Ian Acworth3
1
LMS, Inc., 2SendaAnalytical Technologies Lab., 3ESABiosciences, Inc.U.S.A.
Summary
The characterization of pharmaceutical salts is critical to the drug development process, for example, in salt
selection, confirmation of stoichiometry and detection of impurities. In general, multiple analytical techniques are
required to address the diverse nature of analytes (inorganic, organic, anionic, cationic, absorbtivity, hydrophobicity,etc.). The objective of this study was to investigate the use of HPLC with Charged Aerosol Detection (CAD) as a
generic approach to this broad range of analytes. A zwitterionic stationary phase was operated in HILIC mode using
a acetonitrile-water mobile phase pH buffered with ammonium acetate. CAD response was obtained for all analytes,
with or without a chromophore. Our initial studies demonstrated the ability to analyze commonly used inorganic
positive and negative counter-ions simultaneously along with several active pharmaceutical ingredients (APIs).
Limits of detection were in the low ng range with linear response over at least 3 orders of magnitude and intra-assay
precision <3% RSD. These data demonstrate the capability to quantify a wide range of analytes that are relevant topharmaceutical formulation development and characterization.
Keywords: Charged Aerosol Detection ; CAD ; HILIC ; counter-ion ; APIs
1 Introduction
The need to analyze inorganic cations and anions stretches across many fields, ranging from pharmaceuticalformulations and product characterization, to environmental analysis. Ion chromatograph with the electric conductivity
detector (ICCD) is used mostly for inorganic ion analysis today. Ion chromatography techniques by their very design
do not permit the simultaneous analysis of anions and cations in a single run.
In this study, we used Merck (SeQuant) polymeric Zwitterionic column (ZIC-pHILIC) and binary gradient systemand separated inorganic cations and anions, organic acids and bases, APIs and Counter-ions and detected them byCorona CAD , UV, and LCMS system. All the data presented here were obtained without changing mobile phasecomposition or column.
2 Materials and Methods
Column: Merck (SeQuant) ZIC-pHILIC; 4.6 x 150 mm, 5 µm (Merck)
Column temperature: 30oC
Mobile phase A: 15 % 100 mM ammonium acetate, pH 4.68, 5 % methanol, 20 % IPA, 60 % acetonitrile
Mobile phase B: 50 % 30 mM ammonium acetate, pH 4.68, 5 % methanol, 20 % IPA, 25 % acetonitrile
Gradient: T=0 min 20 %B, T=3 min 20 %B, T=24 min 70% B, T=26 min 70 %B, T=32min 15 %B, T=34 min 20 %B,
T=40min 20 %B
Flow rate: 0.5 mL/min、Injection volume: 10 µL、Sample vial: polypropylene
3 Results and Discussion
In this study, we showed that the quantitative analysis of an inorganic and organic counter-ions, API salts and theimpurities of the w/w level of 0.1% was possible by a single chromatographic method. The Corona CAD approach isable to measure both anions and cations simultaneously, on a single platform. It offers both time and cost savings whencompared to conventional ICCD approaches. The Corona CAD method uses conditions compatible with LC-MS.
The HPLC-CAD-UV-MS platform can be used to more fully characterize a sample.

Corresponding author, Name, Address, E-mail Address,
Masaaki Senda、 2841-2 Kusahano Akiruno Tokyo Japan 、sendas@crux.ocn.ne.jp

P23
Simultaneous Cation and Anion Analysis with Charged Aerosol Detection
Yasuhiro Kanedai1, Kusuo Hashiguti1, Kyouko Fukushima1, Masaaki Senda1,2
Christopher Crafts3, Jasmine Gray3, Marc Plante3 and Ian Acworth3
1
LMS, Inc., 2SendaAnalytical Technologies Lab., 3ESABiosciences, Inc.U.S.A.
Summary
Quantitative analysis of anions and cations is an important aspect of drug development and quality control.
This includes confirmation of stoichiometry, counter-ion identity and completeness of pharmaceutical salt
formation as well as detection of ionic impurities. Ion chromatography is often used for these analyses but avariety of specialized columns, ion suppressors and modes of operation are required to address the range ofanalytes of interest. In this study, hydrophilic interaction chromatography (HILIC) was used in combination withcharged aerosol detection (CAD). A polymeric zwitterionic stationary phase operated in HILIC mode allowed
separation of anions and cations in a single chromatographic run.
Keywords : HPLC Universal Detection ; Charged Aerosol Detection ; anions and cations
Ion chromatography
1 Introduction
Ion chromatography with conductivity detection (ICCD), is the most common approach for the measurement ofions. ICCD typically uses a weak ionic resin for its stationary phase and a high ionic strength mobile phase. An
additional neutralizing suppressor column is often required to remove background eluent ions. ICCD cannot
measure both anions and cations simultaneously, so either the operator must wait for a considerable period whenswitching chemistries or multiple instruments must be used. Due to the amount of time to recondition the column
and detector, gradient methods are typically not implemented with ICCD. In this study, it was shown that themobile phase conditions of the pH, buffer strength and organic modifier concentration could be manipulated toeffect a given separation. The results demonstrate that the present method can readily measures the ionic
impurities and the counter ions, etc. and can become a powerful substitution for conventional ion chromatography.
2 Materials and Methods
The use of a binary gradient HPLC system in this study allows for the analysis of a range of anions and cations(ex. chloride, nitrate, sulfate, phosphate, sodium, potassium).
Column: Sequant ZIC-pHILIC; 4.6 x 150mm, 5µm(Merck)
Column temperature : 30oC
Mobile phase A : 15% 100mM Ammonium Acetate, pH 4.68, 5% Methanol, 20% IPA, 60% Acetonitrile
Mobile phase B : 50% 30mM Ammonium Acetate, pH 4.68, 5% Methanol, 20% IPA, 25% Acetonitrile
Flow rate: 0.5 mL/min
Detector: CoronaCAD (ESA Bioscience inc.)3 Results and Discussion
The method, without sample extractions, can determine ion concentrations in the high ppb range, with sufficientaccuracy and precision to meet pharmaceutical testing requirements. Ion analyses were shown to be quantifiable
over a wide range of concentrations, covering 800ppb to 100ppm. LOD (limits of detection) and LOQ (limits ofquantification) of each ion were 1.3~7.0 ng and 4.0~12.0 ng as mass on column. The amount of variance at the12.5-ppm points was found to be less than 5 % RSD over a 7 day period, indicating that the method is alsoprecise. Minor adjustments to the gradient allowed marked improvement in ion resolution without the need forchanging mobile phase composition, illustrating the chromatographic power of this approach.
Corresponding author, Name, Address, E-mail Address,
Masaaki Senda、 2841-2 Kusahano Akiruno Tokyo Japan 、sendas@crux.ocn.ne.jp

P24
Feature of new organic synthesis chiral polymer as HPLC stationary
phase.
Takeshi Inoue, Tsutomu Yamaguchi, Keiko Hasegawa.
Tokyo Chemical Industry Co.,Ltd. Chromatgraphy Department
TEL 03-3927-0193
Summary

6-15-9 Toshima Kita-ku Tokyo 114-0003 Japan

FAX 03-3927-0226 E-mail t-inoue@tokyokasei.co.jp

Polymaleimide derivative spiral structure has great ability of chiral separation. We applied thispolymer as HPLC stationary phase.

It is suitable for the chiral separation of a wide range of substrates

including carbonyl (ketones, esters, carboxylic acids, amino acid derivatives), alcohols and others. We thinkpolymaleimide derivative nitrogen atom concern chiral recognition of carbonyl groups. This stationary phaseworks not only normal phase but also reversed phase mode.
Key ward: HPLC, chiral separation, polymer phase, carbonyl compound
Introduction

In many cases, HPLC chiral separation columns apply for analysis enantiomer excess of chiralcompounds. It has some kinds of stationary phase, for example, polysaccharide, cyclodextrin, crown ether andsmall molecule optical compounds. Those columns have a good performance to certain compounds but somestationary phases do not work wide range compounds. We used polymaleimide derivatives as HPLC stationary
phase and it worked wide range chiral compounds especially carbonyl compounds. We introduce performance of
this new stationary phase as HPLC column.
Materials and Methods 76 kinds of Carbonyls (ketones, esters, carboxylic acids, amino acid derivatives),
alcohols and other chiral compounds used as test analyte of chiral separation. Analytical mode is normal phase(Hexane/IPA) and reversed phase (Acetonitrile/Water).
Result and Discussion 76 chiral compounds analysis by this new type HPLC columns. It includes many kindsof carbonyl compounds. The most successful separation is ketones and esters. This polymaleimide derivatives
chiral stationary phase has nitrogen atom in spiral structure. Carbonyl compounds come close to nitrogen area ofpolymaleimide derivatives spiral. One of racemic form is easy to come close spiral area and other racemic form
is difficult to come close. So, this spiral polymer has ability of chiral recognition of carbonyl compounds, wethink.

P25
Development of a single-step ELISA capillary
by enzyme proximity-dependent reaction
Erina Tsutsumi, Terence G. Henares, Hiromi Yoshimura, Yao Toshio and Hideaki Hisamoto
Osaka Prefecture University, JAPANSummary
A single-step enzyme-linked immunosorbent assay (ELISA) capillary for capillary-assembled microchip(CAs-CHIP) is developed. This ELISA capillary involves dual immobilization strategies of antibodies andenzyme proximity-dependent reaction. Inside the capillary, first, glucose oxidase (GOD) and 1st antibody (Ab)were covalently immobilized, then peroxidase (POD)-labeled 2nd Ab was non-covalently immobilized. When thesample solution containing antigen, glucose, amplex red and ascorbic acid enters into the capillary via capillary
force, the POD-labeled 2nd Ab releases from the wall of the capillary, which ultimately trapped on the surface ofthe capillary as a sandwich immunocomplex. Then, H2O2 released by enzyme reaction of glucose/GOD smoothly
react with amplex red/POD and generate resorufin having red fluorescence. When the antigen is not contained in
the sample solution, POD-labeled 2nd Ab in bulk is inhibited by ascorbic acid. Therefore the conversion of
amplex red to resorufin is reduced. Here preliminary experiment to demonstrate this concept was carried out.
Key word: capillary, capillary-assembled microchip, ELISA, microchip, sensor
1 Introduction
ELISA is one of the most efficient and effective clinical diagnostic tools for the determination of various
biomolecules related to certain disease. Its miniaturization may lead to minimal reagents/sample consumption
and faster immunoreaction in a microspace. Generally, microfluidic immunosorbent assay involve washing steps
and incubations with antigen/antibody. Although sensitive and selective, the complicated fluid handling inherent
to such bioanalytical assay may be time-consuming. In this study, we developed a new single-step ELISA
capillary allowing simple analysis of proteins.
2 Materials and Methods
A single-step ELISA capillary(square, I.D.100mm×100mm) was prepared by covalently immobilizing GOD andanti-human IgG. Then HRP-labeled anti-human IgG was immobilized non-covalently with the aid ofpoly(ethylene)glycol serving as a scaffold. The sample solution contains sample (human IgG), glucose, amplex
red and ascorbic acid, and introduced into single-step ELISA capillary via capillary force. All single-step
capillary characterizations were done using a fluorescence microscope.
3 Result and Discussion
Before single-step ELISA experiments, preliminary experiments to demonstrate enzyme proximity-dependent
reaction were carried out. When the capillary immobilizing GOD and anti-human IgG was treated with thesample solution(human IgG),2nd Ab solution, then the reagent mixture solution(glucose, amplex red and ascorbicacid), step by step, increase of fluorescence intensity was observed. On the other hand, when the reagent mixture
solution containing 1000 times higher concentration of 2nd Ab was directly introduced into the same capillary,fluorescence intensity was weaker than that obtained in the former experiment, although the 2nd Ab concentration
was much higher. These results suggest that the enzyme proximity-dependent effect was involved in reaction
mechanism. Futhermore, when our initial concept of single-step ELISA was carried out, it was confirmed thequantative measurement for the different human IgG concentration in the ng/mL range was possible.

P26
COMBINABLE-PDMS CAPILLARY (CPC) SENSOR ARRAYTOWARDS ALL SINGLE-STEP ASSAY OF
MULTIPLE ANALYTES ON A SINGLE MICROFLUIDIC DEVICE
Kozo Akai, Terence G. Henares, Yosuke Uchiyama, Fumito Okubo, Toshio Yao, and Hideaki Hisamoto
Osaka Prefecture University, JAPANSummary
In this study, we fabricated the Combinable-PDMS Capillary (CPC) sensor allowing single step assay by simply
introducing a sample solution by capillary force. CPC is composed of a convex-shaped PDMS plate
immobilizing undissolvable reagents and a concave-shaped PDMS plate immobilizing dissolvable reagents.
Since the concave-shaped PDMS has a deeper channel size compared to that of convex structure, combining
these PDMS plates allowed easy fabrication of capillary structure possessing different reagents inside the same
capillary. This method is useful for immobilizing two different reagents which reacts each other. As
applications, we carried out an enzyme inhibition assay and a competitive immunoassay using the CPCs.
Key word: combinable-PDMS capillary(CPC), immunoassay, enzyme / antigen / antibody immobilization
1 Introduction
In order to make the biochemical assay “single-step” using a capillary, immobilization of both biologicalreagents and organic/inorganic small molecule reagents are often required, however, in some cases, it istechnically very difficult since these species react each other during the immobilization procedure (i.e.,
antigen-antibody, enzyme-substrate….etc). To solve this problem, we propose the use of CPC that assembles two
independent PDMS structures immobilizing specific reagents to form the capillary. This capillary-type sensor canbe easily arrayed to fabricate multiplexed sensor array. In order to demonstrate the usefulness of CPCs, an
enzyme inhibition assay and a competitive immunoassay were chosen as examples.
2 Materials and Methods
Fabrication of PDMS capillary was demonstrated in
Figure 1A. Two different PDMS molds varying in
dimensions were used to create convex-shaped andconcave-shaped PDMS plates. For enzyme inhibition
assay, fluorescent substrates and trypsin, and forcompetitive immunoassay, HRP-labeled antibody andantigen, GOD, were immobilized on concave-shaped
PDMS and convex-shaped PDMS, respectively.
Combining these two PDMS plates formed the PDMS
capillary.
3 Result and Discussion
Figure 1. shows the typical fabrication procedure and resulting CPC array containing different fluorescentsolutions. CPC sensors for different analytes can be easily arrayed to fabricate multiple-sensing array. For
enzyme inhibition assay, principle of operation was confirmed by difference of fluorescence response to sample
solutions with and without inhibitor. For competitive immunoassay, principle was confirmed in a similar mannerusing antibody sample solutions. Here, other preliminary results will be presented.

P27
In situ monitoring of fast chemical processes under the hydrothermal
conditions
Yasuda Tomoko1, Hiroki Nagayoshi1, Toshio Yao1 and Kunio Kawamura1
1
Osaka Prefecture University, Japan
Summary

Recently, we have established the capillary flow hydrothermal reactor system for the UV-vis
absorption spectrophotometer (CHUS) for monitoring reactions within 0.002 – 200 s attemperatures up to 400 ℃. To investigate the scope of CHUS, we observed the oxidation of
benzyl alcohol (PhCH2OH) to benzaldehyde (PhCHO) and benzoic acid (PhCOOH) and theheat stability of DNA. Using CHUS, the present study demonstrates the capability andusefulness of CHUS for hydrothermal applications in practical and fundamental areas.
Key word: Hydrothermal reaction; in situ UV-vis spectrophotometry; Alcohol oxidation; Stability of DNA
1 Introduction

Hydrothermal reactions are becoming important both in fundamental and practical areas. For
the industrial and environmental applications of these reactions, the reduction of resourcesand energy consumptions are desirable. In addition, these processes are interested infundamental studies regarding the origin of life and geochemical problems. Here, we show thecapillary flow hydrothermal reactor system for the UV-vis absorption spectrophotometer(CHUS), which enables to monitoring reactions within 0.002 – 200 s up to 400 ℃. 1) By using
CHUS, we have successfully monitored the reaction behaviors of peptides and nucleic acids. In
the present study, we successfully applied CHUS for the oxidation of benzyl alcohol.
2 Materials and Methods

The CHUS system consists of a high-pressure pump, a high temperature reactor, atemperature controller, a pressure regulator, a UV-vis absorption spectrophotometer, and acooling bath. A fused-silica capillary, of which a detection window was made for in situ UV-vis
observation, is settled in the reactor. The behaviors of nucleic acids were observed within 5 150 s at 150 – 330 ℃. The reactions of the oxidation of benzyl alcohol were monitored within
0.64 – 61.6 s at 300 ℃ and below using an aqueous solution containing PhCH2OH, Na2WO4and H2O2.
3 Result and Discussion<Behaviors of nucleic acids> It was observed that double-stranded DNA was converted tosingle-stranded DNA (ssDNA) at temperatures over 100 ℃, ssDNA became insoluble andthen degraded monomers at over 225 ℃.2)
<Oxidation of benzyl alcohol> The aqueous solution, mentioned above, prepared 11 %benzaldehyde (PhCHO) and 0.3 % benzoic acid (PhCOOH) at 300 ℃ in 0.64 s, and 4.5 %PhCHO and 0.1 % PhCOOH at 200 ℃ in 61.6 s. In the reaction at 300 ℃, an in situ
monitoring of the formation of PhCHO from PhCH2OH was succeeded at the wavelength of
maximum absorption for PhCHO (250 nm).
1) Patent 3378936
2) K. Kawamura and H. Nagayoshi, Thermochim. Acta, 466, 63 (2007).
K. Kawamura; Gakuen-cho 1-1, Sakai, Osaka; Kawamura@chem.osakafu-u.ac.jp

P28
Introduction of high selective and high sensitive
Reduction Gas Detector (RGD) for GC
Takaaki Murata, Masaaki Noguchi(Techno International Co. Japan) Tsuneaki Maeda(AIST Japan)
Summary
There are some detectors that measure reducing gases, the SRI Reduction Gas Detector (RGD) is the mostsensitive detector available for hydrogen, carbon monoxide, and other reducing gases. Low ppb detection limits
are achievable for hydrogen. Detection limits in the ppt level are achievable for carbon monoxide.
The carbon monoxide and hydrogen cause HgO with the reductive reaction, and mercury vapor is generated.
The mercury vapor is measured with the UV lamp.
Materials and Methods
The RGD detector uses a mercuric oxide reaction tube and a mercury lamp in a heated UV detector cell. The
reaction tube is heated to 260-300℃. Located immediately downstream of the reaction tube, the UV detector cellis heated to 170℃. The UV detector cell is equipped with a mercury lamp and a UV photodiode. The gaseous
mercury absorbs the UV light from the mercury lamp as it flows through the cell.

Result and Discussion
The following two chromatograms were produced with an SRI RGD equipped GC. Room air samples werediluted with nitrogen in tedlar bags, then injected by gas sampling valve onto the Molecular Sieve packed
column.

H2 level in atmospheric air is ca.500ppb.

This system can be detected around 25 ppb H2 in air.
Analytical Parameters:
Valve injection; 1 mL sample loop
Column: Molecular Sieve 13X
1/8 in.o.d., 2 meter long,
Carrier gas, helium at 5 mL/min.
RGD gain: High
Reactor temperature: 290℃
Detector temperature: 170℃
Valve temperature: 60℃
Concentration at 50 ppb, Results: upper,
Component Ret.time(min.)Area (count)Hydrogen

2.433

100.8250

Oxygen3.500

796.4090

Concentration at 25 ppb, Results: lower
Component Ret.time (min.)Area (count)Hydrogen

2.450

55.2755

Oxygen3.516

571.6580