Environment

Environmental
Page 3 Analysis of 8 kinds of estrogens in environmental water by ultra high performance liquid chromatograph hybrid triple quadrupole mass spectrometer
Page 8 UHPLC-MS/MS, an Alternative Solution to Conventional Biosensor Approach for Quorum Sensing Signaling Molecules Detection in Complex Environmental Samples
Page 14 Simultaneous analysis of anionic, amphoteric and non-ionic surfactants using ultra-high speed LC-MS/MS
Page 20 Multi-component quantitative analysis of pharmaceuticals and personal care products in the environment by LC-MS/MS with fast polarity switching
Page 25 Analysis Method of Polybrominated Diphenyl Ethers Using GC-MS and GC-MS/MS Coupled With an Automated Identification and Quantitation System with a Database
Page 30 The analysis of olefine and aromatic hydrocarbon in hydrocarbon mixture using Multi-Dimensional GC/GCMS system
PO-CON1233E
Analysis of 8 kinds of estrogens in environmental water by ultra high performance liquid chromatograph hybrid triple quadrupole mass spectrometer
IMSC 2012
PMo-039
Hongyuan Hao, Jinting Yao, Luying Zhou, Hengtao Dong, Qiang Li Analytical Applications Center, Analytical Instruments Dept., Shimadzu (China) Co., Limited, Shanghai 200052, China
Introduction
Water environment is the largest repository of environmental estrogens. Estrogen in the natural environment are difficult to be decomposed, but into various animal through the food chain, adverse effects on male reproductive system. Environmental estrogenic substances into the human body, which causes human hormone excess and affects human sex hormones in normal work. Environmental hormones have become the third largest environmental. All the countries in the world are aware of environmental estrogens on environmental and human hazards, and conducted in-depth research. This article use the SHIMADZU ultra performance liquid chromatography LC-30A and three triple quadrupole mass spectrometer coupled LCMS-8030, established a rapid and accurate method for determination of estrogen.
Results and Discussion

100 L of 8 kinds of Estrogens in standard solution was injected, the standard solution was separated in 5 minutes, and the MRM chromatogram was showed in Fig.1. The calibration curve information, the limits of quantification (LOQ) and the limits of detection quantification (LOD) for the method of 8 kinds of Estrogens were investigated, and the results were showed in Table 2. The sample concentration and the peak area showed excellent linear relationship, with a coefficient of determination greater than 0.999. The repeatability 8 kinds of Estrogens in different concentration were investigated, and the area RSD and retention time RSD (%) were less than 4.843% and 0.638%, respectively, as showed in Table 3. The spiked sample (17- Estradiol and Ethinyloestradiol, 2 ng/LOthers,1 ng/L) were analyzed, and results showed in Fig. 2, which showed high sensitivity for detection of Estrogens.
Experimental
HPLC The analyses were performed on a Shimadzu Nexera UHPLC instrument (Kyoto, Japan) equipped with LC-30AD pump, CTO-30A column oven, DGU-30A3 degasser, and SIL-30AC auto injector. Column: Shimadzu Shim-pack XR-ODS III 2.0 mm75 mm. 1.6 m Mobile phase: A water;B ACN / MeOH = 1/1 (v/v) Flow rate: 0.4 mL/min Column oven: 40C Injection volume: 10 L Gradient program: showed in table 1
Mass spectrometry A triple quadruple mass spectrometer (Shimadzu LCMS-8030, Kyoto, Japan) was connected to the Shimadzu fast-analytical UHPLC instrument via an ESI interface. Interface: Interface voltage: Nebulizing gas: Drying gas: Collision gas: DL: Heat block: Acquisition Pause time Dwell time ESI + 4.5 kV N2 , 3 L/min N2 , 15 L/min Ar2 250C 400C MRM mode 3 ms 10 ms
Table 1 LC Gradient Program
Time (min) 1.50 4.00 4.50 5.00 5.10 7.00
B.Conc 55 60 100 100 45
1:287.30>171.20(-)(5.00) 2:271.30>145.10(-)(5.00) 30000 4:295.30>145.20(-)(15.00) 5:269.30>145.15(-) 6:267.25>251.15(-) 25000 7:269.25>134.20(-) 1 8:265.25>93.10(-) 20000 15000 10000 5000
4
5 6
0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 min
Fig. 1 Chromatogram of Estrogen Standards (100 g/L) 1-Estriol2-17-Estradiol3-17-Estradiol4-Ethinyloestradiol5-Estrone6-Diethylstilbestrol7-Hexoestrol8-Dienoestrol Table 2 Calibration curve informations of Estrogen s
No. 1 2 3 4 5 6 7 8
Name Estriol 17-Estradiol 17-Estradiol Ethinyloestradiol Estrone Diethylstilbestrol Hexoestrol Dienoestrol
Calibration curve Y = (0.120659)X Y = (0.146104)X Y = (0.0709176)X Y = (0.039812)X Y = (0.392514)X Y = (0.129798)X Y = (0.199119)X Y = (0.175211)X
correlation coefficient Linearity range r g/L 0.9998 0.9999 0.9998 0.9999 0.9999 0.9999 0.9999 0.9998 1-100 1-100 2-100 1-100 1-100 0.5-500 0.5-500 0.5-500
LOD (ng/L) 0.05 0.25 0.65 0.60 0.30 0.15 0.20 0.15
LOQ (ng/L) 0.15 0.75 1.95 1.80 0.90 0.45 0.60 0.45
Table 3 Repeatability of Estrogen s with different concentration (n=6)
No. 1 2 3 4 5 6 7 8
RSD%5 g/L Area R.T 3.160 4.236 4.843 4.401 4.007 4.753 2.372 1.159 0.638 0.323 0.240 0.454 0.241 0.271 0.034 0.194
RSD%20 g/L Area R.T 2.448 1.318 4.354 4.675 1.818 0.929 0.868 1.079 0.135 0.084 0.080 0.084 0.051 0.079 0.080 0.058
RSD%100 g/L Area R.T 1.801 1.852 1.816 2.846 1.146 0.864 1.463 0.981 0.122 0.053 0.057 0.097 0.051 0.059 0.057 0.095
Fig. 2 Chromatogram of spiked sample (17- Estradiol and Ethinyloestradiol, 2 ng/LOthers,1 ng/L )
Conclusions
A LCMS/MS method has been developed for the chemical analysis of 8 kinds of Estrogens in water were detected by Shimadzu Nexera UHPLC and LCMS-8030 triple quadruple mass spectrometer. All of them were separated in 5 minutes. The linear range was from 0.5 to 500 g/L with correlation coefficients (r) more than 0.999. Retention times and peak areas results were highly reproducibility. The limit of quantification (LOQ) were less than 2 ng/L for all of Estrogens. This method is rapid, efficient and highly sensitive for quantitative analysis of 8 Estrogens in environmental water.
First Edition: September, 2012
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PO-CON1247E
UHPLC-MS/MS, an Alternative Solution to Conventional Biosensor Approach for Quorum Sensing Signaling Molecules Detection in Complex Environmental Samples
IMSC 2012
1,3
PTh-025
Chuan Hao (Grant) Tan, 3Kai Shyang Koh, 1,2 Yan Zhou, 1,3,4Scott A Rice, 3,4Staffan Kjelleberg, 1,2 Wun Jern Ng, 5Peiting Zeng, 5Zhaoqi Zhan 1 Advanced Environmental Biotechnology Centre, 2 Nanyang Environment and Water Research Institute, 3 Singapore Centre on Environmental Life Sciences Engineering, Nanyang Technological University, Singapore, 4 The Centre for Marine Bio-Innovation, The University of New South Wales, Australia; 5 Customer Support Centre, Shimadzu (Asia Pacific) Pte Ltd, Singapore
Introduction
Quorum sensing (QS) signaling is critical for coordinating the social behaviors of bacteria, i.e., regulating biofilm development[1]. Acylhomoserine lactones (AHLs) consist of a homoserine lactone ring and an acyl side chain, at variable lengths, oxidation states and saturation levels, are the most common signals employed by the bacteria. As AHLs are highly susceptible to elevated temperatures, alkaline conditions, and are often degraded rapidly by other microbes living within the same niche, it is always a real challenge to characterize and quantify AHLs in the natural environments[2]. Conventionally, AHLs are detected by biosensor-dependent assays, which are time-consuming and with limited sensitivity detecting all range of AHLs[3]. Here, a UHPLC-MS/MS method is developed to overcome the limitations of the biosensor-based AHL detection.
Fig. 1 General chemical structure of AHLs where R represents functional groups (H, O or OH) and n represents 1-15 carbons.
Materials and Methods

Naturally occurring AHLs, from the activated sludge of a lab-scale bioreactor system, were extracted by dichloromethane. The samples extracted were analysed on UHPLC-MS/MS tandem quadrupole system (Shimadzu LCMS-8030) using a Shim-pack XR-ODS column (2 100 mm, 2.2 m). A total of thirteen synthetic AHLs, ranging from C4 to C14, with various oxidation states, were used as reference AHLs for the analysis. Automatic MRM optimization was applied to each standard to determine the MRM transitions for subsequent sample analysis. A pair of MRM transitions was selected for each standard. The MRM transition that exhibited higher intensity was used for quantification analysis, while the other for confirmation of the AHL identity. In addition, MS full scan coupled with synchronized survey scan was employed to identify possible existence of other AHL structures with predicted m/z values.
In situ detection of AHLs in activated sludge samples
Fig. 2 Detection of AHLs present in situ in activated sludge samples using biosensor Escherichia coli pJBA357 (To be continued)
Fig. 2 (Continued). Co-incubation of live activated sludge (A) and heatinactivated sludge (B) with the biosensor for 4 hours at room temperature. The presence of AHLs is
indicated by the expression of green fluorescent proteins by the biosensors, which can be visualized using confocal laser scanning microscope (CLSM).
MRM analysis of thirteen synthetic AHL standards
Fig. 3 MRM chromatogram for thirteen synthetic AHLs. Table 1 Synthetic AHLs used as standard reference for analysis.
Peak
C4 -H C6 -OXO C6 -H C8 -OXO C7 -H C8 -H C10 -OXO
AHL identity
N-butyryl-DL-homoserine lactone N-(3-Oxohexanoyl) -DLhomoserinelactone
Peak
C10 -H C12 -OXO
AHL identity
N-decanoyl-DL-homoserine lactone N-(3-oxododecanoyl)-Lhomoserinelactone N-(3-hydroxydodecanoyl)-Lhomoserinelactone N-dodecanoyl-DLhomoserine lactone N-(3-oxotetradecanoyl)-Lhomoserinelactone N-(3-oxotetradecanoyl)-Lhomoserine lactone
N-hexanoyl-DL-homoserine C12 -OH lactone N-(3-oxooctanoyl) -Lhomoserine lactone C12 -H
N-heptanoyl-DL-homoserine C14 -OXO lactone N-octanoyl -DL-homoserine lactone N-(3-oxodecanoyl)-Lhomoserine lactone C14 -H
Fig. 4. Representatives of standard calibration curves for different synthetic AHLs spiked to the blank sample matrix. The limit of detection (LOD) for all the thirteen synthetic AHLs were found to be approximately 0.1 ppb to 1.0 ppb.
Case study 1 Activated sludge samples (Ulu Pandan, Sg)

A)
S1 S2 S3 C 6-OXO L1 L2 L3 L4 L5
C 8-OXO
C 10-OXO
B)
Fig.5 Detection of AHLs in activated sludge samples by two different approaches - Thin layer chromatography separation followed by detection using biosensor Agrobacterium tumefaciens A136 (A) and LCMS-8030 (B). Each of the AHLs identified in LCMS chromatogram (B) was quantified (C) based on the standard calibration curves generated in Fig. 4.
AHL Concentration (ppb)
C)
50 45 40 35 30 25 20 15 10 5 0
Case study 2 Bacterial isolates from the activated sludge

A) B)
Fig. 6 Detection of AHLs in overnight culture of bacteria isolated from the activated sludge by two different approaches - Thin layer chromatography separation followed by detection using biosensor Chromobacterium violaceum CV026 (A) and LCMS-8030 (B). Note that only the AHL profile of bacteria isolate R092R is displayed in the LCMS chromatogram (B).
Case study 3 Detection of AHL structures with predicted m/z values

MS full scan coupled with synchronized survey scan approach was employed to detect possible existence of other AHL structures beyond the thirteen synthetic AHL standards. A combination criteria of predicted
211.2
retention time, and m/z values for both parent and product ions were included to confirm the identity of the compound.
Inten.(x10,000,000) 1.00 0.75 0.50

213.2 229.2 230.2 216.1 227.2 245.2 212.2 246.2
A)
MS
Parent ion m/z
0.25 0.00 210.0
215.0
102.2
220.0
225.0
230.0
235.0
240.0
245.0
247.2
m/z
Inten.(x100,000)
B)
2.0 1.5 1.0

83.2
MS/MS Specific product ion m/z

111.1 212.1
0.0 50 100 150 200 250 300 350 m/z
Fig 7 Detection of AHLs with predicted m/z values in R092R isolate using MS synchronized survey scan. Expected parent ion, m/z 230.2, was detected by MS scan mode (A) and MS fragmentation pattern of the target mass peak (B).
74.2
230.1
0.5
Table 2 Detection of AHLs with predicted m/z values and retention time.
Peak
1 2 3
Retention time (min)

3.463 7.964 7.340
Parent ion (m/z)

230.2 340.5 354.5
Product ion (m/z)

102.2 102.2 102.1
Putative AHL identity

C7 -OH C16 -H C16 -OXO
Conclusions
Advantages of using UHPLC/MS/MS over conventional biosensor approach in detection of AHL signaling molecules from complex environmental samples : Rapid, quantitative, high resolution, high throughput and highly sensitive Wide dynamic detection range Universal detection limit for all different AHL structures - Unbiased assessment Able to identify possible existence of AHL structures with predicted m/z values
Reference
1. Koutsoudis et al. 2006. Quorum-sensing regulation governs bacterial adhesion, biofilm development, and host colonization in Pantoea stewartii subspecies stewartii. Proc. Natl. Acad. Sci. USA 103:5983-5988 2. Wang et al. 2005. Rapid acyl-homoserine lactone quorum signal biodegradation in diverse soils. Appl. Environ. Microbiol. 71:1291-1299 3. Van der Meer et al. 2010 Where microbiology meets microengineering: design and applications of reporter bacteria. Nat. Rev. Microbiol. 8:511-522
PO-CON1212E
Simultaneous analysis of anionic, amphoteric and non-ionic surfactants using ultra-high speed LC-MS/MS
IMSC 2012
PTh-048
Keiko Matsumoto1, Jun Watanabe1, Junko Iida1 1 Shimadzu Corporation.1, Nishinokyo-Kuwabaracho Nakagyo-ku, Kyoto 6048511, Japan
Introduction
Surfactant chemistry has made a considerable impact on a number of household products including detergents, shampoos and toothpaste. Products are generally classified by the type of each hydrophilic substructure into anionic, cationic, amphoteric and non-ionic surfactants. Either anionic or non-ionic surfactants are typically used as synthetic detergents, however, to better elucidate the
C nH (2n+1)
potential risk in environmental samples, mainly in agricultural soils and sediments, methods need to take into account a range of surfactant chemistries. Current surfactant monitoring methodologies tend to focus on a specific surfactant. Here, we have developed the simultaneous analysis method for typical anionic, amphoteric and non-ionic surfactant using LC-MS/MS.
CH 3 H 3C
SO 3H
O O
-
(CH 2) nCH 2
CH 3
Betain (n=10,12,14) LAS (n=10 -14)
H (OCH2CH2) 7 O
(CH2) 11 CH 3
Heptaethyleneglycoldodecylether
Fig. 1 Structure of anionic, amphoteric and non-ionic surfactant
Methods and Materials

Commercially available surfactants were used for this experiment. Standards of surfactants were diluted with water / acetonitrile =3/7 to an appropriate concentration and then analyzed by LC-MS/MS. As an LC-MS/MS system, UHPLC was coupled to triple quadrupole mass spectrometer (Nexera MP with LCMS-8040, Shimadzu Corporation, Kyoto, Japan). Separation was achieved using a YMC-Triart C8 column (100 mmL., 2.0 mmI.D., 1.9 um particles) and column oven temperature was maintained at 40C. Samples were eluted at flow rate 300 uL/min with a binary gradient system; the mobile phase consisted of (A) 10 mM ammonium acetate buffer and (B) mixture of 10 mM ammonium acetate / acetonitrile / isopropanol (1/4/5). LC-MS/MS with electrospray ionization was operated in multiple-reaction-monitoring (MRM) mode with ultra-fast polarity switching.
High Speed Mass Spectrometer Ultra Fast Polarity Switching 15 msec Ultra Fast MRM Max. 555 transition /sec
Fig. 2 LCMS-8040 triple quadrupole mass spectrometer
Results
Method development for surfactants
The following standard surfactants were selected and analyzed; anionic surfactant: linear alkylbenzene sulfonate (LAS) C10-C14 mixture, amphoteric surfactant: EMPIGEN BB Detergent (Betaine) C10, C12, C14 mixture (Sigma-Aldrich, St.Louis, MO), and non-ionic surfactant: heptaethyleneglycoldodecylether (HEDE). Full scan measurement by flow injection analysis (FIA) was conducted to determine the optimum ionization polarity of target compounds followed by MRM transition optimization by FIA. As a consequence, all LASs were detected as the de-protonated ions (M-H) in negative ion mode and m/z 183 was selected as the product ion of MRM transitions for all LASs (C10-C14). All Betaine were detected as protonated ions (M+H) in positive ion and m/z 104 was selected as the product ions of MRM transitions for all Betaines (C10, C12 and C14). HEDE yielded the protonated ion (M+H) in positive ion as the precursor and m/z 133 was selected as product ion for MRM transition. As compounds selected in this experiment formed either positive or negative ion, high-speed polarity switching is an important element to consider in developing an optimized LC-MS/MS method.
UHPLC conditions (Nexera MP system) Column: YMC TriartC8 100 mm2.0 mm, 1.9 um Mobile phase A: 10 mM Ammonium acetate B: 10 mM Ammonium acetate / Acetonitrile/ isopropanol (1/4/5) Flow rate: 0.3 mL/min Time program: B conc.75%(0 min) -95%(1.5-3 min) - 75%(3.01-5 min) Injection vol.: 10 uL Column temperature: 40C MS conditions (LCMS-8040) Ionization: ESI, Positive/Negative MRM mode
Table 1 MRM transition of LAS 9 surfactants Compound LAS C10 LAS C11 LAS C12 LAS C13 LAS C14 Betain C10 Betain C12 Betain C14 HEDE Polarity + + + + MRM transition 297.15 > 182.60 311.20 > 182.60 325.20 > 182.70 339.20 > 182.60 353.40 > 182.60 271.95 > 103.80 300.00 > 103.70 328.20 > 103.70 495.30 > 133.15
Fig. 3 shows MRM chromatograms of the nine surfactants. It took 5 minutes per one LC-MS/MS analysis, including column rinsing, and excellent separation and high sensitive detection were obtained.
LAS C10 (-) LAS C11 (-)
Betain C10 (+) LAS C12 (-)

250000 225000 200000 175000 150000 125000 100000 75000 50000 25000 0 1.00 1.25 1.50 1.75 2.00
Betain C12 (+)
LAS C13 (-) LAS C14 (-) Betain C14 (+) HEDE (+)
2.25
2.50
min
Fig. 3 Mass Chromatograms of typical anionic, amphoteric and non-ionic surfactant (concentration of each compound : 5 ppb)
The dilution series of these compounds were analyzed. All compounds were detected at ppb level with excellent linearity (Table 2, Fig. 4).
Table 2 Linearity 9 surfactants Compound LAS C10 LAS C11 LAS C12 LAS C13 LAS C14 Betain C10 Betain C12 Betain C14 HEDE Polarity 1-500 ppb 1-500 ppb 1-500 ppb 1-500 ppb 0.5-100 ppb 1-100 ppb 1-100 ppb 1-100 ppb 1-100 ppb Coefficient (r2) 0.998 0.999 0.997 0.999 0.998 0.999 0.999 0.999 0.999
Area 2000000 1500000 1000000 500000 0 0.0
Betain C10
Area 175000 150000 125000 100000 75000
Area
HEDE
10000000 7500000 5000000
LAS C13
1-100 ppb R2=0.999

25.0 50.0 75.0 ppb
50000 25000 0 0.0 25.0
1-100 ppb R2=0.999

50.0 75.0 ppb
2500000 0 0
1-500 ppb R2=0.999

100 200 300 400 ppb
Fig. 4 Representative calibration curve (Betain C10, HEDE, LAS C13)
Quantitative Analysis of real world sample

The quantitative analysis of real world sample using the kitchen detergents and liquid soap was achieved using this method. Kitchen detergents and liquid soap was diluted 1000 to 1 with water / acetonitrile= 3/7. Finally, it was filtered through a 0.2 um filter and analyzed by LC-MS/MS. MRM chromatograms of each surfactants in the kitchen detergents and liquid soap is shown Fig. 5,6.
liquid soap (1000) LAS C10 (-) LAS C11 (-) LAS C12 (-)
The 1000 to 1 dilution of liquid soap contained approximately 5 to 6 ppb LAS C12 and C13. Therefore, it was determined that undiluted liquid soap contains 5 to 6 ppm LAS C12 and C13. On the other hand, undiluted kitchen detergent contains approximately 40 ppm LAS C10, C11, C12 and C13, and approximately 75 ppm HEDE.
LAS C13 (-)

50000 25000 0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 min
LAS C10 LAS C11 LAS C12 LAS C13 LAS C14 HEDE Betain C10 Betain C12 BetainC14
Concentration (ppb) < 1 ppb < 1 ppb 4.9 ppb 6.1 ppb no detection no detection no detection no detection no detection
Fig. 5 Measurement results of liquid soap (dilution 1000 times)

Kitchen detargent (1000) LAS C10 (-) LAS C12 (-)
500000 400000 300000 200000 100000 0 0.0
LAS C11 (-)
LAS C13 (-)
HEDE(+) matrix
LAS C10 LAS C11 LAS C12 LAS C13 LAS C14 HEDE Betain C10 Betain C12 BetainC14
Concentration (ppb) 75.2 ppb no detection no detection no detection no detection 35.7 ppb 31.0 ppb 40.4 ppb 44.3 ppb
0.5
1.0
1.5
2.0
2.5
3.0
min
Fig. 6 Measurement results of Kitchen detergent (dilution 1000 times)
Conclusions
Typical anionic, amphoteric and non-ionic surfactant were separated with high resolution within 2.5 minute. Even though selected compounds formed either positive or negative ion, all surfactants were detected with high sensitivity. High-speed polarity switching is an important element for simultaneous analysis of various surfactants. This method was able to be applied to the quantification of surfactants in kitchen detergents and liquid soap.
PO-CON1213E
Multi-component quantitative analysis of pharmaceuticals and personal care products in the environment by LC-MS/MS with fast polarity switching
IMSC 2012
PTh-050
Natsuyo Asano, Kiyomi Arakawa, Shinjiro Fujita, Kazuo Mukaibatake, Ichiro Hirano SHIMADZU CORPORATION, Kyoto, Japan
Introduction
Pharmaceuticals and personal care products (PPCPs) constitute a group of emerging contaminants which have received considerable attention in recent years. Monitoring of PPCPs in the environment is vital as many of these compounds are ubiquitous, persistent and biologically active with recognised endocrine-disruption functions. Given the hazardous nature of these compounds, there is a need to provide fast and sensitive multi-residue methods that are able to analyze multiple classes of compound within one analytical procedure. Here we report a new multi-residue UHPLC-ESI-QqQ method that utilizes fast polarity switching with an optimized chromatographic gradient that removes matrix effects and results in excellent ng/L detection levels. Furthermore, we have evaluated the performance of polarity switching in comparison to dedicated single polarity experiments.
Materials and Methods

Natural river and lake water was collected from the Shiga region (Japan) and spiked, without any sample
Table 1 Analytical conditions. UHPLC LC system: Analysis Column: Mobile Phase A: Mobile Phase B: Gradient Program: Flow rate: Column Temperature: Injection Volume: MS MS system: Ionization: Nebulizing Gas Flow: Curtain Gas Flow: Heating Gas Flow: Probe Temperature : HSID Temperature :
pre-treatment, at a range of concentration levels (1 10000 ng/L) with 15 PPCPs.
Nexera (Shimadzu, Japan) Shim-pack XR-ODSIII (2.0 mmI.D. x 50 mmL., 1.6 m) 0.1% Formic acid - Water Acetonitrile 0%B (0-6 min) 80%B (16 min) 100%B (16.01-18 min) 0%B (18.01-21 min) 0.4 mL/min 40C 40 L
LCMS-8080 (Shimadzu, Japan) ESI (positive/negative) 3.00 3.50 12.00 450C 300C
A higher sensitivity triple quadruple mass spectrometer (LCMS-8080, Shimadzu, Japan) operating in SRM mode
with fast polarity switching (20 msec) was used for the detection of positively and negatively charged analytes.
Results
Analysis of PPCPs spiked in environmental water
As a result of the complex matrix in which PPCPs are present, the occurrence of ion suppression/enhancement can reduce MS/MS detection limits. For this reason, an optimized gradient was developed that focused target analytes at the head of the chromatographic column while allowing the interfering environmental matrix to be eluted (Fig. 1).
Before the organic phase was increased, the aqueous mobile phase held at 100% for 6 min.
Fig. 1 Gradient program of LC.
All compounds were measured by SRM with fast polarity switching (20 msec) for multi-component analysis. Excellent limits of quantification were achieved in the range 1 50 ng/L for nearly all studied compounds, with outstanding
linearity (R2 > 0.999). The analysis results of 15 PPCPs are shown in Table 2, Fig. 2 shows calibration curves for three selected PPCPs: Carbamazepine, Albeterol and Ibprofen.
Table 2 MRM mode parameters and analysis results for each PPCPs. Compound Albuterol Acetaminophen Trimethoprim Sulfamethoxazole Carbamazepine Dehydronifedipine Naproxen Antipyrine Doxycycline Isopropylantipyrine Warfarin Ibuprofen Gemfibrozil Triclocarban Triclosan Polarity pos pos pos pos pos pos pos pos pos pos pos neg neg neg neg neg Transition 240.20>148.20 152.10>110.30 291.20>230.20 254.00>92.30 237.10>194.20 345.20>284.10 231.10>185.20 189.00>56.20 445.00>428.00 231.00>189.00 309.00>163.00 307.00>161.20 205.30>161.40 249.30>121.30 313.10>160.20 287.00>34.90 LOQ (ng/L) River 5 50 5 25 1 5 10 10 100 2.5 5 25 50 25 25 50 Lake 5 50 25 50 2.5 25 25 25 50 5 10 50 50 50 25 100 %Recoery (100 ng/L) River 148 80 143 104 94 97 99 106 79 103 86 91 106 114 120 105 Lake 112 87 118 76 68 75 76 82 56 82 60 103 87 77 98 74
(a) Carbamazepine
Area (100,000) 8.0 1 100 ng/L R 2 = 0.9996 6.0
(b) Albuterol
Area (100,000) 3.0 2.5 2.0 5 1000 ng/L R 2 = 0.9994
(c) Ibprofen
Area (100,000) 1.75 1.50 1.25 50 5000 ng/L R 2 = 0.9999
4.0
1.00 1.5 0.75 1.0 0.5 0.50 0.25 0 250 500 750 Conc. (ng/L) 0 0 1000 2000 3000 4000 Conc. (ng/L)
2.0
0 0.0 25.0 50.0 75.0 Conc. (ng/L)
Fig. 2 Calibration curves for Carbamazepine (a), Albeterol (b) and Ibprofen (c); (a) was spiked in river water, (b) and (c) were spiked in lake water.
Polarity Switching
To evaluate the capability of polarity switching the data quality obtained was compared to dedicated positive or negative analysis. Data quality obtained during polarity switching experiments was directly comparable to that achieved during dedicated
(a) Polarity Switching: 20 ms
15.0 104
1: Carbamazepine (pos) 2: Dehydronifedipine (pos)
positive or negative analysis (Fig. 3). Long term stability was investigated by making 100 injections over 10 hours. Polarity switching data indicates excellent stability over the analysis time (Fig. 4, Table 3).
(b) Non-polarity Switching

15.0 104
1: Carbamazepine (pos) 2: Dehydronifedipine (pos)
15.0
104
3: Gemfibrozil (neg) 4: Triclocarban (neg)
Intensity
Intensity
4: Triclocarban (neg)
Intensity
10.0
3: Gemfibrozil (neg)
10.0
10.0
5.0
5.0
5.0
0 1.50 2.00 2.50 3.00 min
0 1.50 2.00 min
0 2.75 3.00 min
Fig. 3 Comparison of polarity switched analysis (a) and non-polarity switched analysis (positive only or negative only analysis) (b).
10 5
3.0
100 injections (10hours)

2.5
Carbamazepine Dehydronifedipine Gemfibrozil Triclocarban
2.0 Area
1.5
1.0
0.5
0 0 20 40 Injection 60 80 100
Fig. 4 Results for area variation across the 100 serial analyses.
Table 3 Analysis results for respective compounds. Compound 1 2 3 4 Carbamazepine Dehydronifedipine Gemfibrozil Triclocarban Polarity pos pos neg neg Transition 237.10 > 194.20 345.20 > 284.10 249.30 > 121.30 313.10 > 160.20 %RSD 2.70 3.94 3.10 3.52
Conclusion
Optimization of the LC gradient program resulted in the reduction of matrix effect and the recoveries of 70 120% for almost all studied compounds. Using LCMS-8080, excellent sensitivity and linearity were obtained for PPCPs spiked in environmental water samples. Fast polarity switching results were shown to be comparable to dedicated single polarity experiments for the analysis of PPCPs in environmental samples.
PO-CON1214E
Analysis Method of Polybrominated Diphenyl Ethers Using GC-MS and GC-MS/MS Coupled With an Automated Identification and Quantitation System with a Database
IMSC 2012
PTh-060
Katsuhiro Nakagawa, Tomoaki Kondo, Kouki Tanaka, Yuki Sakamoto, Shuichi Kawana, Haruhiko Miyagawa Shimadzu Co., Kyoto, Japan
Introduction
There are 209 isomers of polybrominated diphenyl ethers (PBDE), each with varying levels of toxicity and detection frequency in environmental samples. A common method for analysis of PBDEs requires expensive C13-labeled standards and a gas chromatograph coupled to a high resolution magnetic sector mass spectrometer (GC-HRMS). The operation of GC-HRMS instruments requires a highly skilled analyst, and maintenance can be time-consuming and labor-intensive. This poses a critical situation, especially for environmental laboratories in developing countries. Kadokami et al. [1] developed a novel automated identification and semi-quantitation database (AIQS-DB) which allows automatic identification and semi-quantitation of 1,000 pollutants without requiring analysis of standards. The database includes retention indices, mass spectra, and internal calibration curves for 1,000 environmental pollutants. The pollutants are identified using the mass spectrum and retention time (RT) predicted by retention index. Semi-quantitation is performed using internal calibration curve. This poster illustrates a method for analysis of PBDE using the database. To minimize the use of costly internal standards, the AIQS-DB was applied to PBDE with lower toxicity and detection frequency, while the conventional method (isotope dilution) was applied to PBDEs with a higher toxicity and detection frequency to obtain precise quantitation results. Single quadrupole GC-MS could be used for some samples, however the sediment samples had complex, interfering co-extractants which hindered detection of the PBDE. Samples with interfering matrices were analyzed on a triple quadrupole GC-MS/MS. Using the GC-MS/MS, the PBDE were successfully identified, and analysis results corresponded to concentrations of PBDE determined by the conventional HR-GCMS method.
1. Novel gas chromatography-mass spectrometry database for automatic identification and quantification of micropollutants, Kiwao Kadokami, Kyoko Tanada, Katsuyuki Taneda, Katsyhiro Nakagawa, J. Chromatogr A, 1089 pp 219-226, 2005.
Results
Evaluation of AIQS-DB
Accuracy of predicated RT was evaluated using analytical standards with three different GC-MS instruments, and a real sample.
Table 1 Accuracy of prediction RT for standards on three different instruments (A, B, and C)
RT=predicted - measured RT RT [min] A B Tri/ BDE-028 0.04 -0.07 Tetra/ BDE-47 0.05 -0.06 Penta/ BDE-100 0.08 -0.03 Penta/ BDE-99 0.07 -0.04 Hexa/ BDE-154 0.08 -0.03 Hexa/ BDE-153 0.08 -0.02 Hepta/ BDE-183 0.09 -0.03 Deca/ BDE-209 0.08 -0.04
Compound
Table 2 Accuracy of prediction RT for real sample

Compounds Tri/ BDE-028L Mono/ BDE-001 Di/ BDE-010 Tri/ BDE-028 Tetra/ BDE-47L Tetra/ BDE-51 Penta/ BDE-99L Penta/ BDE-105 Hexa/ BDE-153L Hexa/ BDE-140 Hepta/ BDE-183L Hepta/ BDE-190 RT [min] 0.09 0.09 0.08 0.08 0.12 0.09 0.14 0.13 0.03 0.08 0.07 0.11
C -0.03 -0.02 0.01 0.00 0.00 0.01 0.00 -0.01
Semi-quantitation results for sediment sample spiked with PBDEs at 50 ng/mL.

Compounds Mono/ BDE-001 Di/ BDE-010 Tri/ BDE-028 Tetra/ BDE-51 Penta/ BDE-105 Hexa/ BDE-140 Hepta/ BDE-190 Conc. 64.2 64.0 68.5 62.9 53.7 60.7 169.9 ng/mL
The maximum difference in RT was 0.14 min. Semi-quantitation results were from 68.5 to 53.7 ng/mL, except hepta/ PBDE-190. PBDE-190 co-eluted with an interference and could not be accurately quantified
Experimental
Target compounds
Conventional method
ID 1 2 3 4 5 6 7 8 Compound Tri/ BDE-028 Tetra/ BDE-47 Penta/ BDE-99 Penta/ BDE-100 Hexa/ BDE-153 Hexa/ BDE-154 Hepta/ BDE-183 Deca/ BDE-209 IS C12 Tri/ BDE-028L Tetra/ BDE-47L Penta/ BDE-99L Penta/ BDE-100L Hexa/ BDE-153L Hexa/ BDE-154L Hepta/ BDE-183L Deca/ BDE-209L
13
AIQS -DB
ID 9 10 11 12 13 14 15 16 17 18 Compound Mono/ BDE-001 Mono/ BDE-002 Mono/ BDE-003 Di/ BDE-007 Di/ BDE-008 Di/ BDE-010 Di/ BDE-011 Di/ BDE-012 Di/ BDE-013 Di/ BDE-015 ID 19 20 21 22 23 24 25 26 27 28 Compound Tri/ BDE-017 Tri/ BDE-025 Tri/ BDE-028 Tri/ BDE-030 Tri/ BDE-032 Tri/ BDE-033 Tri/ BDE-035 Tri/ BDE-037 Tetra/ BDE-049 Tetra/ BDE-051 ID 29 30 31 32 33 34 35 36 37 38 Compound Tetra/ BDE-066 Tetra/ BDE-071 Tetra/ BDE-075 Tetra/ BDE-077 Tetra/ BDE-079 Penta/ BDE-085 Penta/ BDE-105 Penta/ BDE-116 Penta/ BDE-118 Penta/ BDE-119 ID 39 40 41 42 43 44 45 46 47 Compound Penta/ BDE-120 Penta/ BDE-126 Hexa/ BDE-128 Hexa/ BDE-138 Hexa/ BDE-140 Hexa/ BDE-155 Hexa/ BDE-156 Hepta/ BDE-181 Hepta/ BDE-190
Sample preparation
Preparation of samples
- 10 grams dried sediment
Extract cleanup
- Florisil cleanup
Soxhlet extraction
- Toluene 100 mL, 20 hours
Concentration and solvent exchange
-Solvent exchange to 100 L nonane
Concentration GC-MS/MS Back-with acid
- 50 mL 98% H2SO4 2, 50 mL NaCl (aq) - 30 grams sodium sulfate - Reduce to 3 mL -Addition of 1 gram activated copper powder (60 mesh). -Solvent exchange to 1mL hexane (+toluene)
Concentration
Solvent exchange Sulpher removal
SHIMADZU GCMS-TQ8030
GC-MS/MS Analysis
Table 4 Repeatability of the analysis (n=5; 10 ng/mL, Deca-BDE: 100 ng/mL) and linearity of calibration curve (10, 20, 50, 100, 500 ng/mL (Deca BDE; X10)
Compounds Tri/ BDE-028 Tetra/ BDE-47 Penta/ BDE-100 Penta/ BDE-99
StDev 0.2355 0.4045 0.4639 0.3707
%RSD 2.40 4.01 4.65 3.77
R 0.99999 0.99993 0.99997 0.99998
Compounds Hexa/ BDE -154 Hexa/ BDE -153 Hepta/ BDE-183 Deca/ BDE -209
StDev 0.247 0.210 0.591 3.664
%RSD 2.43 2.14 5.84 3.94
R 0.99997 0.99998 0.99997 0.99962
(x100,000) 405.80 245.90 3.0
(x10,000) 483.70 2.0 643.60 1.5
(x100,000) 799.50 1.25 959.40 1.00 0.75
GC -MS
2.0
1.0 0.50 0.5
1.0
0.25
11.5
12.0
12.5
13.0
23.0
23.5
24.0
24.5
37.0
37.5
38.0
38.5
(x10,000) 405.80>245.90 5.0 405.80>247.90 4.0
(x10,000) 643.60>483.70 643.60>485.70 4.0 3.0
(x100,000) 959.40>799.30 7.5 959.40>801.30
GC -MS/MS
3.0 2.0 1.0 2.0
5.0
2.5
1.0
11.5
12.0
12.5
13.0
23.0
23.5
24.0
24.5
37.0
37.5
38.0
38.5
Tri-BDE (28)
Hexa-BDE (153)
Deca-BDE (209)
Fig. 1 Chromatograms of selected PBDEs in sediment using GC-MS and GC-MS/MS
Analytical conditions
GC-MS :GCMS-TQ8030
Ion Source Temp. Interface Temp. Solvent Cut Time Ionization Voltage Emission Current Acquisition Mode :230C :300C :1 min :70 eV :150 A :SIM (GC-MS) MRM (GC-MS/MS) Column :Rtx - 1614 (15 m 0.25 mm I.D., 0.10 mm) Injection Mode :Splitless Sampling Time :1 min Injection Volume :1 L Injection Temp. :320C Column Oven Temp. :140C (3 min), 5C /min to 320C (5 min) Carrier Gas :He Flow Control Mode :Linear Velocity (47.9 cm/sec) Purge Flow :5 mL/min High Pressure Injection :150 kPa (1.2 min)
AIQS-DB
RTs of n-alkanes Retention Index Quantitation and confirmation ions Mass spectrum Calibration curve Database for Compound Composer software Data processing parameters for quantitation
RT prediction
Table 5 Comparison of quantitation results of PBDEs in sediment using GC-MS, GC-MS/MS, and GC-HRMS
BDE-** GC-MS GC-MS/MS GC-DMS
Tri Tetra Penta Penta Hexa 28 47 100 99 154 0.45 4.89 1.51 6.45 0.78 0.52 4.94 1.55 6.39 0.92 0.48 4.78 1.35
[ng/g] Hexa Hepta Deca 153 183 209 1.77 1.88 112.58 1.84 1.90 104.10
2.04 99.45
6.19 0.93 1.90
Gas chromatographytriple quadrupole mass spectrometry (GC-MS/MS) was applied to the analysis of PBDEs in a complex sediment sample matrix, ensuring accurate identification and low-level detection. Using the GC-MS/M,
the PBDE were successfully identified, and analysis results corresponded to concentrations of PBDE determined by the conventional HR-GCMS method.
Conclusion
1. To minimize the use of costly internal standards, the AIQS-DB was applied to PBDE with lower toxicity and detection frequency, while the conventional method (isotope dilution) was applied to PBDEs with a higher toxicity and detection frequency to obtain precise quantitation results. 2. For complex matrices such as sediment, GC-MS/MS was used to selectively detect PBDE in the presence of co-extractants. 3. The results show that the developed method can be applied to analysis of PBDE in sediment.
PO-CON1235E
The analysis of olefine and aromatic hydrocarbon in hydrocarbon mixture using Multi-Dimensional GC/GCMS system
IMSC 2012
PTh-160
Li-Bin Liu,Fu-Rong Wang, Gui-Xiang Yang, Tao-Hong Huang, Lei Cao Shimadzu (China) Co., Ltd. 6F, Life Tower, No.16 Chaoyang Men Wai Street, Beijing, China 100020
Introduction
The component of hydrocarbon mixture is very complicated, including even and odd number carbon hydrocarbon. Its analysis with conventional gas chromatographic approaches is a big challenge and can give us inaccurate or even false results because overlapping is always happened. Many measures were taken to avoid interferences, such as improving sample preparation or using high selectivity detectors. Multi-dimensional GC/GCMS system with multiple heart-cutting is one of the powerful tools. Multi-dimensional GC/GCMS can improve resolution beyond that of the regular GC analysis as it re-introduces the dissolved component of interest into another column. In other words, only part of the peak of the component that was insufficiently separated on the column where the sample initially passed through (called the 1st column) is introduced (heart-cut) to a column of another type (called the 2nd column), so that insufficiently separated components can be separated. A device called a switching device is used for heart-cut introduction of peaks eluted from the 1st column to the 2nd column. As a switching device, the recently developed Multi-Deans switching unit can be used in combination with a GC-FID as the first analytical dimension and a GCMS as the second analytical dimension. The analytes pass the first column and are detected in the FID (stand-by mode) or are transferred to the second column and analyzed with mass spectrometer or GC detector such as FID (cut mode). By using this system, complicated matrix analysis such as hydrocarbon mixture was done to demonstrate MDGC/GCMS system performance.
FID INJ
MS
column
2nd
1st
column
Switching device
Fig. 1 Multidimensional GC/GCMS system
[Stand - by Mode]
Pressure ( P2)
[Cut Mode]
Pressure ( P2)
APC
Valve Pressure P
APC
Valve
PressureP
Pressure ( P1) PressureP PressureP P1 1st Column Sample
P P2 P P1
PressureP-P2
Presure ( P1)
PressureP P1 1st Column Sample
2 Column
nd
2 Column
nd
1st DET
1st DET
Fig. 2 Schematic diagram of the Multi-Deans switching device
Instrumentation and operational conditions

The Shimadzu MDGC system consisted of two GC-2010 gas chromatographs (defined as GC 1 and GC 2), an MS-QP2010 quadrupole mass spectrometer with an AOC-20i autosampler (Shimadzu Corporation, Kyoto, Japan). One-dimensional GC analytical conditions: Inlet: 280C; Injection mode: split (split ratio 50); Injection volume: 0.2 ul; Carrier gas: helium; Carrier gas control: constant pressure 186.7 kPa; Column 1: HP-1 (30 m 0.25 mm 0.25 um) Column temperature:60C (3 min) 10C / min 170C 1C / min 205C 10C / min 290C (10 min) FID temperature: 300C; Hydrogen flow rate: 40 ml / min; Air flow rate: 400 mL / min; Makeup gas (He) flow rate: 5 mL / min; Switching pressure:121.1 kPa ; Two-dimensional GCMS analytical conditions: Column 2: Rtx-2330 (60 m 0.32 mm 0.2 um) Ion source temperature: 200C; Interface temperature: 230C; Scan Mode: SCAN; Scan range: 35-400 m/z; Cutting program: Cutting C17 non-normal alkane (22.99-26.06 min; 26.68-27.99 min) Cutting C18 non-normal alkane (28.03-30.66 min; 31.71-32.90 minCutting C19 non-normal alkane 32.91-36.03 min; 37.00-38.47 min) Cutting C20 non-normal alkane 38.52-42.24 min; 42.95-50.00 min) Column 2 temperature-programmed condition when cutting C17 non-normal alkane: 40C (3 min) 3C/min 100C (10 min) 10C/min 210C (10min) Column 2 temperature-programmed condition when cutting C18 non-normal alkane: 40C (3 min) 3C/min 100C (6 min) 0.5C/min 110C 10C/min 220C (10 min) Column 2 temperature-programmed condition when cutting C19 non-normal alkane : 40C (3 min) 2C/min 110C (10 min) 5C/min 140C 10C/min 230C (10 min) Column 2 temperature-programmed condition when cutting C20 non-normal alkane: 40C (3 min) 2C/min 110C (10 min) 5C/min 140C 10C/min 230C (10 min)
Results and Discussion

uV (x10,000) Chromatogram 4.0
C 17
C 18 C 19
3.5
3.0
2.5
C 16 C 20
2.0
1.5
1.0
0.5
0.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 min
Fig. 3 Not cutting, one-dimensional GC spectrum.
6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
(x1,000,000) TIC 9.0 8.0
(x1,000,000) TIC
Aromatics Olefin
7.0 6.0 5.0 4.0 3.0 2.0 1.0
Olefin Aromatics
30.0
32.5
35.0
37.5
40.0
42.5
45.0
35.0
37.5
40.0
42.5
45.0
47.5
50.0
52.5
55.0
Fig. 4 Two-dimensional GCMS spectrum of cutting C17 non-normal alkane (22.99-26.06 min; 26.68-27.99 min).
(x1,000,000) 2.75 TIC 2.50 2.25 2.00 1.75 1.50 1.25 1.00 0.75 0.50 0.25 0.00 -0.25 45.0
(x100,000) 3.00 TIC 2.75
Aromatics Olefin
Olefin Aromatics
2.50 2.25 2.00 1.75 1.50 1.25 1.00 0.75 0.50
47.5
50.0
52.5
55.0
57.5
60.0
47.5
50.0
52.5
55.0
57.5
60.0
The quantitative results are based on the area normalization method, the total content of the isomerization, olefins and aromatics with same carbon numbers is calculated with the one-dimensional result; the
percentage of the isomerization, olefins and aromatics is calculated respectively with the two-dimensional result. The result show that the total content of olefin is 6.64%, the total content of aromatic is 0.67%.
Conclusion
This MDGC/GCMS system can analyze the olefine and aromatic hydrocarbon in hydrocarbon mixture. It has superiority on the determination of the complicated matrix sample in order to obtain more reliable analytical results.

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Results and Discussion

Time (min) 1.50 4.00 4.50 5.00 5.10 7.00

B.Conc 55 60 100 100 45

Name Estriol 17-Estradiol 17-Estradiol Ethinyloestradiol Estrone Diethylstilbestrol Hexoestrol Dienoestrol

Table 3 Repeatability of Estrogen s with different concentration (n=6)

First Edition: September, 2012

Materials and Methods

In situ detection of AHLs in activated sludge samples

MRM analysis of thirteen synthetic AHL standards

N-hexanoyl-DL-homoserine C12 -OH lactone N-(3-oxooctanoyl) -Lhomoserine lactone C12 -H

Case study 1 Activated sludge samples (Ulu Pandan, Sg)

AHL Concentration (ppb)

Case study 2 Bacterial isolates from the activated sludge

Case study 3 Detection of AHL structures with predicted m/z values

Inten.(x10,000,000) 1.00 0.75 0.50

Parent ion m/z

0.25 0.00 210.0

2.0 1.5 1.0

MS/MS Specific product ion m/z

0.0 50 100 150 200 250 300 350 m/z

Retention time (min)

Parent ion (m/z)

Product ion (m/z)

Putative AHL identity

First Edition: September, 2012

Methods and Materials

Betain C10 (+) LAS C12 (-)

Betain C12 (+)

Area 2000000 1500000 1000000 500000 0 0.0

Area 175000 150000 125000 100000 75000

10000000 7500000 5000000

1-100 ppb R2=0.999

50000 25000 0 0.0 25.0

1-100 ppb R2=0.999

1-500 ppb R2=0.999

Fig. 4 Representative calibration curve (Betain C10, HEDE, LAS C13)

Quantitative Analysis of real world sample

LAS C13 (-)

Fig. 5 Measurement results of liquid soap (dilution 1000 times)

LAS C11 (-)

LAS C13 (-)

Fig. 6 Measurement results of Kitchen detergent (dilution 1000 times)

First Edition: September, 2012

Materials and Methods

pre-treatment, at a range of concentration levels (1 10000 ng/L) with 15 PPCPs.

Fig. 1 Gradient program of LC.

0 0.0 25.0 50.0 75.0 Conc. (ng/L)

(b) Non-polarity Switching

0 1.50 2.00 2.50 3.00 min

0 1.50 2.00 min

0 2.75 3.00 min

100 injections (10hours)

Carbamazepine Dehydronifedipine Gemfibrozil Triclocarban

First Edition: September, 2012

Table 2 Accuracy of prediction RT for real sample

C -0.03 -0.02 0.01 0.00 0.00 0.01 0.00 -0.01

Semi-quantitation results for sediment sample spiked with PBDEs at 50 ng/mL.

- 10 grams dried sediment

- Toluene 100 mL, 20 hours

Concentration and solvent exchange

-Solvent exchange to 100 L nonane

Concentration GC-MS/MS Back-with acid

Solvent exchange Sulpher removal