Analysis Guidebook: Environmental Analyses

C180-E058A
Analysis
Guidebook Environmental
Analyses
Index
2.26 Analysis of PCB in Water (1) - GC ------------------------------------------------------- 56
Analysis of PCB in Water (2) - GC ------------------------------------------------------- 57
1. Drinking Water 2.27 Analysis of Residual Organic Phosphorus Compounds (1) - GC --------------------- 58
Analysis of Residual Organic Phosphorus Compounds (2) - GC --------------------- 59
2.28 Analysis of Volatile Organic Compound (VOC) in Wastewater and Environment Water using Head Space Method (1) - GC/MS ---- 60
1. 1 Analysis of Anions in Tap Water (1) - Ion Chromatograph ----------------------------- 1 Analysis of Volatile Organic Compound (VOC) in Wastewater and Environment Water using Head Space Method (2) - GC/MS ---- 61
Analysis of Anions in Tap Water (2) - Ion Chromatograph ----------------------------- 2 2.29 Analysis of Volatile Organic Compound (VOC) (P/T Method) - GC/MS ------------- 62
1. 2 Analysis of Cations in Tap Water (1) - Ion Chromatograph ---------------------------- 3 2.30 Analysis of Estradiol - GC/MS ------------------------------------------------------------ 63
Analysis of Cations in Tap Water (2) - Ion Chromatograph ---------------------------- 4
1. 3 Analysis of Anions in Tap Water - PIA-1000 --------------------------------------------- 5
1. 4 Analysis of Volatile Organic Compound (VOC) in Tap Water (1) - Purge & Trap GC/MS ----- 6 W3. Wastewater
Analysis of Volatile Organic Compound (VOC) in Tap Water (2) - Purge & Trap GC/MS ----- 7
1. 5 Analysis of Musty Smelling Components in Tap Water (1) - Purge & Trap GC/MS ------ 8
Analysis of Musty Smelling Components in Tap Water (2) - Purge & Trap GC/MS ------ 9
1. 6 Analysis of Musty Smelling Components in Tap Water (HS Method) - GC/MS ---- 10 3. 1 Analysis of Anions in Wastewater - Ion Chromatograph ------------------------------ 64
1. 7 Analysis of Musty Smelling Components in Tap Water (SPME Method) - GC/MS ----- 11 3. 2 Analysis of Cations in Wastewater - Ion Chromatograph ----------------------------- 65
1. 8 Analysis of Acrylamide in Water (1) - GC,GC/MS -------------------------------------- 12 3. 3 Analysis of Anions in Wastewater - PIA-1000 ------------------------------------------ 66
Analysis of Acrylamide in Water (2) - GC,GC/MS -------------------------------------- 13 3. 4 Analysis of Cations in Wastewater - PIA-1000 ----------------------------------------- 67
1. 9 Analysis of Golf Course Agrochemicals - GC/MS -------------------------------------- 14 3. 5 Analysis of Volatile Organic Compound (VOC) in Wastewater - GC ----------------- 68
1.10 Analysis of Ethylenediamine Tetraacetic Acid (EDTA) - GC/MS ---------------------- 15
1.11 Analysis of Non-organic Components in Tap Water (1) - ICP-AES ------------------ 16
Analysis of Non-organic Components in Tap Water (2) - ICP-AES ------------------ 17
1.12 Analysis of Non-organic Components in Mineral Water (1) - ICP-AES -------------- 18 4. Atmosphere
Analysis of Non-organic Components in Mineral Water (2) - ICP-AES -------------- 19
1.13 Direct Analysis of As in Tap Water and River Water - AA ----------------------------- 20
1.14 Direct Analysis of Pb in Tap Water and River Water - AA ----------------------------- 21 4. 1 Analysis of Acidic Substances in Exhaust Gas - Ion Chromatograph ---------------- 69
4. 2 Analysis of Exhaust Gas Absorption Solution - PIA-1000 ----------------------------- 70
4. 3 Analysis of Tolylenediisocyanate (TDI) in Work Environment Monitoring (1) - HPLC ------- 71
Analysis of Tolylenediisocyanate (TDI) in Work Environment Monitoring (2) - HPLC ------- 72
2. Environment Water 4. 4 Analysis of Aldehyde/Ketonic products in Exhaust Gas - HPLC --------------------- 73
4. 5 Analysis of Aldehyde/Ketonic products in Room Atmosphere (1) - HPLC ---------- 74
Analysis of Aldehyde/Ketone in Atmosphere (2) - HPLC ------------------------------ 75
2. 1 Analysis of Anions in River Water (1) - Ion Chromatograph -------------------------- 22 4. 6 Analysis of Aldehyde Types in Atmosphere (1) - GC ---------------------------------- 76
Analysis of Anions in River Water (2) - Ion Chromatograph -------------------------- 23 Analysis of Aldehyde Types in Atmosphere (2) - GC ---------------------------------- 77
2. 2 Analysis of Cations in River Water (1) - Ion Chromatograph ------------------------- 24 4. 7 Analysis of Formaldehyde in Room Atmosphere - UV --------------------------------- 78
Analysis of Cations in River Water (2) - Ion Chromatograph ------------------------- 25 4. 8 Analysis of Volatile Organic Components (VOC) in Atmosphere(1) - Solid-phase Adsorption & Thermal Desorption GC/MS ----- 79
2. 3 Analysis of Anions in Lake Water - Ion Chromatograph ------------------------------ 26 Analysis of Volatile Organic Components (VOC) in Atmosphere (2) - Solid-phase Adsorption & Thermal Desorption GC/MS ---- 80
2. 4 Analysis of Cations in Lake Water - Ion Chromatograph ------------------------------ 27 4. 9 Analysis of Volatile Organic Components (VOC) in Atmosphere (1) - Container Collection Method GC/MS ----- 81
2. 5 Analysis of Anions in River Water - PIA-1000 ------------------------------------------ 28 Analysis of Volatile Organic Components (VOC) in Atmosphere (2) - Container Collection Method GC/MS ----- 82
2. 6 Analysis of Cations in River Water - PIA-1000 ----------------------------------------- 29 4.10 Automatic Analysis of Micro Amount of N2O in Atmosphere - GC ------------------- 83
2. 7 Analysis of Calcium and Magnesium in River Water - AA ----------------------------- 30 Analysis of Non-organic Elements in Atmosphere Dust (1) - ICP-AES -------------- 84
2. 8 Analysis of Total Nitrogen and Total phosphorus in River Water - UV -------------- 31 4.11 Analysis of Non-organic Elements in Atmosphere Dust (2) - ICP-AES -------------- 85
2. 9 Direct Analysis of Cd and Cr in Seawater - AA ----------------------------------------- 32
2.10 Analysis of Non-organic Components in River Water (1) - ICP-MS ----------------- 33
Analysis of Non-organic Components in River Water (2) - ICP-MS ----------------- 34
2.11 Analysis of Anions in Hot Spring Water - Ion Chromatograph ----------------------- 35 5. Industrial Waste
2.12 Analysis of Cations in Hot Spring Water (1) - Ion Chromatograph ------------------ 36
Analysis of Cations in Hot Spring Water (2) - Ion Chromatograph ------------------ 37
2.13 Analysis of Anions in Rainwater - Ion Chromatograph -------------------------------- 38 5. 1 Screening of Waste Plastic Material using Horizontal ATR (1) - FTIR --------------- 86
2.14 Analysis of Cations in Rainwater - Ion Chromatograph ------------------------------- 39 Screening of Waste Plastic Material using Horizontal ATR (2) - FTIR --------------- 87
2.15 Analysis of Anions in Rainwater - PIA-1000 -------------------------------------------- 40 5. 2 Analysis of Non-organic Elements in Eluate of Incineration Ash (1) - ICP-AES ---- 88
2.16 Analysis of Cations in Rainwater - PIA-1000 ------------------------------------------- 41 Analysis of Non-organic Elements in Eluate of Incineration Ash (2) - ICP-AES ---- 89
2.17 Analysis of Sulfurous Acid Ions in Rainwater - HPLC --------------------------------- 42 5. 3 X-ray Fluorescence Spectrometric Analysis of Industrial Waste (Sludge) - XRF --- 90
2.18 Analysis of Anions in Snow Water - Ion Chromatograph ----------------------------- 43
2.19 Analysis of Anions in Sea Water - HPLC ------------------------------------------------ 44
2.20 Analysis of Ammonia Ions in Sea Water - HPLC --------------------------------------- 45 O6. Others
2.21 Analysis of Fluoride Ions in Sea Water (1) - Ion Chromatograph -------------------- 46
Analysis of Fluoride Ions in Sea Water (2) - Ion Chromatograph -------------------- 47
2.22 Analysis of Microcystin in Blue-green Algae (1) - HPLC ------------------------------ 48
Analysis of Microcystin in Blue-green Algae (2) - HPLC ------------------------------ 49 6. 1 Analysis of Non-agitated Soil Core Sample using Microscopic FTIR (1) - FTIR ---- 91
2.23 Analysis of Cyanogen Compounds by Chemical Classification (1) - HPLC --------- 50 Analysis of Non-agitated Soil Core Sample using Microscopic FTIR (2) - FTIR ---- 92
Analysis of Cyanogen Compounds by Chemical Classification (2) - HPLC --------- 51 6. 2 Analysis of Volatile Organic Compounds (VOC) in Soil (1) - GC/MS ---------------- 93
2.24 High-Sensitivity Analysis of Bisphenol A in Environment Water (1) - HPLC -------- 52 Analysis of Volatile Organic Compounds (VOC) in Soil (2) - GC/MS ---------------- 94
High-Sensitivity Analysis of Bisphenol A in Environment Water (2) - HPLC -------- 53 6. 3 Easy Analysis of Residual MTBE in Soil (HS Method) - GC --------------------------- 95
2.25 Analysis of Alkyl Mercury Compound (1) - GC ----------------------------------------- 54 6. 4 Analysis of Organic Tin in Seawater and Fish (1) - GC/MS, GC ---------------------- 96
Analysis of Alkyl Mercury Compound (2) - GC ----------------------------------------- 55 Analysis of Organic Tin in Seawater and Fish (2) - GC/MS, GC ---------------------- 97
1. Drinking Water
1.1 Analysis of Anions in Tap Water (1) - Ion Chromatograph
■Explanation ■Pretreatment
In December 1992 amendments were made to the Filtering through a membrane filter (0.45µ m) for ion
Ministerial ordinance related to drinking water quality chromatography
standard, the reference values for fluorine, chlorine and
total nitrite plus nitrate nitrogen were set, and the anion ■Analytical Conditions
chromatograph method was adopted as the analysis method. Instrument : Ion chromatograph (suppressor system)
Also, in 2000, a monitoring item for nitrite nitrogen (5ppb) Column : Shim-pack IC-SA2 (250mm ✕ 4.0mm I.D.)
was newly added to the ordinance. In addition to the above Mobile phase : 12mM sodium hydrogen carbonate
substances, the ion chromatograph also can simultaneously (NaHCO3)
analyze phosphate ions and sulfate ions. 0.6mM sodium carbonate (Na2CO3)
Flow rate : 1.0mL/min
Temperature : 30˚C
Detection : Electric conductivity detector
■Peaks
–
1F 0.083ppm
2 –
2 2 Cl 14.0ppm
–
3 NO3 0.289ppm
0.2 2–
4 SO4 14.6ppm
1
µS/cm
3
10
0
5 10 min
µS/cm
5
4
1 3
0
0 5 10 min
Fig. 1 Analysis example of tap water
1
1.1 Analysis of Anions in Tap Water (2) - Ion Chromatograph
■Pretreatment ■Analytical Conditions

Filtering through a membrane filter (0.45µ m) for ion Instrument : Ion chromatograph
chromatography Column : Shim-pack IC-A3 (150mm ✕ 4.6mm I.D.)
Mobile phase : 8.0mM p-hydroxybenzoic acid
3.2mM Bis-Tris*
Temperature : 40˚C
* Bis-Tris : Bis (2-hydroxyethyl) iminotris
(hydroxymethyl) methane
■Peaks
–
1 CO32 (35mg/L)
–
2 F (0.071mg/L)
3 5 –
3 C1 (10.1mg/L)
–
4 NO3 (1.2mg/L)
2–
5 SO4 (17.8mg/L)
12
0 10 (min)
2
1.2 Analysis of Cations in Tap Water (1) - Ion Chromatograph
Sodium, and calcium and magnesium, etc., as items related to Filtering through a membrane filter (0.45µ m) for ion
properties that tap water have are defined as test subjects chromatography
for hardness in the Japanese water quality standard. The
2001 edition of the Drinking Water Test Method introduces the ■Analytical Conditions
ion chromatograph (IC) method as an anion analysis Instrument : Ion chromatograph
method. In addition to the above substances, the IC method (non-suppressor system)
also is capable of simultaneously analyzing lithium ion, Column : Shim-pack IC-SC1 (150mm ✕ 4.6mm I.D.)
potassium ion and ammonium ion. The acidic operating Mobile phase : 3.0mM sulfuric acid
condition of the non-suppressor system is suitable for Flow rate : 1.2mL/min
separating and detecting ammonium ion. Temperature : 30˚C
References
LC talk, Volume 42 (p6-7)
■Peaks
1 1 Na
+
18.057ppm
+
2K 3.434ppm
30 3 Mg2
+
4.455ppm
2+
4 Ca 23.308ppm
20
µS/cm
4
10
3
2
0 5 10 min
Fig. 3 Analysis example of Tap water
3
1.2 Analysis of Cations in Tap Water (2) - Ion Chromatograph

Filtering through a membrane filter (0.45µ m) for ion Instrument : Ion chromatograph
chromatography Column : Shim-pack IC-C3 (100mm ✕ 4.6mm I.D.)
Mobile phase : 2.0mM oxalic acid
Temperature : 40˚C
■Peaks
+
1 Na 8.25ppm
+
2 NH4 0.01ppm
+
3 K 1.66ppm
+
4 Mg2 2.22ppm
2+
5 Ca 11.85ppm
(min)
Fig. 4 Analysis example of sample with addition of 10ppb of NH4+ in tap water
4
1.3 Analysis of Anions in Tap Water - PIA-1000
This is a tap-water analysis example using the personal ion Filtering through a membrane filter (0.45 µ m) for ion
analyzer PIA-1000. Not only is the PIA-1000 useful chromatography
because of its portability but it also proves effective as a
sub-device in the laboratory. Although a compact model, ■Analytical Conditions
the accuracy of the PIA-1000 is on a par with conventional Instrument : PIA-1000
models, which makes it a potent force in everyday analysis Column : Shim-pack IC-A3(S)
work. Mobile phase : PIA-1000 dedicated anion
analysis mobile phase, IC-MA3-1
■Peaks
–
1 HCO3 (32.83mg/L)
–
2 F (0.130mg/L)
–
3 Cr (12.62mg/L)
–
4 NO3 (0.158mg/L)
2–
5 SO4 (16.49mg/L)
Fig. 5 Analysis example of tap water (PIA-1000)
5
1.4 Analysis of Volatile Organic Compound (VOC) in Tap Water (1) - Purge & Trap GC/MS
■Explanation ■Analytical Conditions

The purge trap method involves purging volatile organic P&T: Tekmer-Dohrmann LSC3000J (No cryofocus)
compound that exists in water using helium or nitrogen gas, Trap tube : GI (TENAX)
holding it in a trap tube, then quickly heating it to induct it Sample purge time : 6min
into a GC/MS column. Nearly all the volatile constituents Desorption : 225˚C, 2min
included in a 5mL sample are concentrated in the trap tube
to enable highly sensitive analysis.
Figure 6 is a SIM chromatograph of the 23 constituent
compounds targeted and individual 0.1µg/L concentrations
of p-bromofluorbenzene (IS). The chart 1 shows the names Shimadzu GCMS-QP5050A
of the targeted compounds and the SIM selected ions. Column : DB-624 60m ✕ 0.32mm I.D.,
1.8µm(df)
References Column temperature : 40˚C(1min)-10˚C/min
(1) Drinking Water Test Method & Explanation, Carrier gas 200˚C(5min)
Japan Water Works Association volume : He 100kPa
(2) Environmental Water Analysis Manual,
Environmental Science Research Group volume
(3) New Wastewater Standards and Other Analysis
Methods,
22
8 14
5 11
12
4
3 10
1
2 6 16
19
18
9 20
7 13 15
17
21
23
8 10 12 14 16 18 20 22 24 26 28 30 32 (min)
Ion set number:1 SIM=1205609
61.00 96.00 84.00 86.00 83.00 85.00 117.00 119.00
78.00 62.00 64.00 97.00
130.00 132.00 63.00 65.00 83.00 85.00 110.00 112.00
91.00 92.00 97.00 166.00 164.00 129.00 127.00
91.00 106.00 173.00 175.00 95.00 174.00 146.00 148.00
Fig. 6 Measuring example of 0.1 µg/L added water
6
1.4 Analysis of Volatile Organic Compound (VOC) in Tap Water (2) - Purge & Trap GC/MS
ID Name SIM Selected Ions ID Name SIM Selected Ions

1 1,1-dichloroethene 96,61 13 cis-1,3-dichloroproene 75,110
2 Dichloromethane 84,86 14 Toluene 92,91
3 trans-1,2-dichloroethane 96,61 15 trans-1,3-dichloropropene 75,110
4 cis-1,2-dichloroethane 96,61 16 1,1,2-trichloroethene 97,99
5 Chloroform 83,85 17 Tetrachloroethene 166,164
6 1,1,1-trichloroethane 97,99 18 Dibromochloromethane 129,127
7 Tetrachloromethane 117,119 19 m,p-xylene 106,91
8 Benzene 78,77 20 o-xylene 106,91
9 1,2-dichloroethane 62,64 21 Bromoform 173,175
10 Trichloroethene 130,132 22 p-bromofluorbenzene(IS) 174,176
11 1,2-dichloropropane 63,62 23 p-dichlorobenzene 146,148
12 Bromodichloromethane 83,85
Chart 1 SIM selected ions
Fig. 7 Purge & trap GC/MS system
7
1.5 Analysis of Musty Smelling Components in Tap Water (1) - Purge & Trap GC/MS

Japanese tap water has an established reputation in the area P&T: Tekmer-Dohrmann LSC3000J
of quality as drinking water; however, in recent years, it has
Trap tube : G1 (TENAX TA)
a musty odor depending on the season. And the substances
Sample purge time : 11min
that cause this musty odor are known to be 2-
Force out : 225˚C, 8min
methylisoborneol and geosmin. The threshold value for the
odors of these compounds is approximately 10ppt, which is
low, and cannot be detected in source state by GC/MS
Shimadzu GCMS-QP5050A
analysis, so the purge trap method, as shown in the drinking
water test method, is used to concentrate the compounds for Column : DB-1701 30m ✕ 0.32mm
analysis by GC/MS. This purge trap method involves I.D. 1µm(df)
forcing the targeted compound into a gas phase using Column temperature : 60˚C(3min)-10˚C(min)
aeration, holding this gas phase in a concentration tube 240˚C(10min)
filled with TENAX TA, then forcing out of the Carrier gas : He 40kPa
concentration tube by heating.
References
(1) Drinking Water Test Method & Explanation,
Japan Water Works Association volume
(2) Environmental Water Analysis Manual,
159058
ID #1 Mass No.: 95.00 Element name: 2-MIB
Surface area = 11829.5 *Concentration + 16926
Contribution ratio = 0.997846
Area 104 Concentration (ppt)
8.0 1 0.500
2 1.000
3 3.000
4.0 4 5.000
95.00
108.00
11.5 12.0 0 2.5 5.0
Conc
31094 ID #2 Mass No.: 112.00 Element name: geosmin
Surface area = 14468.8 *Concentration + 5982.67
Area 104 Concentration (ppt)
8.0 1 0.500
2 1.000
112.00 3 3.000
4.0 4 5.000
126.00
0 2.5 5.0
Conc
14.5 15.0
Fig. 8 Analysis example of musty odor 3.0ppt Fig. 9 Calibration curve

(Upper: 2-MIB, lower: geosmin) (Upper: 2-MIB, lower: geosmin)
8
1.5 Analysis of Musty Smelling Components in Tap Water (2) - Purge & Trap GC/MS
Reference Example 1
CH3 CH3 CH3
CH3
OH
CH3
OH
CH3
2-Methylisobor neol:m/z 95,108 Geosmin:m/z 112.126
Fig. 10 Structures of 2-MIB and geosmin
Fig. 11 Principle diagram of purge & trap method
9
1.6 Analysis of Musty Smelling Components in Tap Water (HS Method) - GC/MS

Japanese tap water has an established reputation in the area HS
of safety as drinking water; however, musty smelling
Sample volume : 10mL + NaCl 3g
components in dam, lake and river surface water that is the
Sample temperature : 80˚C (30 min)
source of tap water has become a summer problem, which
Sample shaker : ON
is being combated through the use of activated carbon. And
the substances that cause this musty odor are 2- GC
methylisoboneol (2-MIB) and geosmin produced via blue-
green algae and actinomycetes. The threshold value for the Column : Rtx-5ms
odors is several ng/L, which is an extremely low (30m ✕ 0.25mm I.D. df = 0.25µm)
concentration, so the solid-phase extraction & GC/MS or Column temperature : 35˚C(2 min)-15˚C/min -250˚C
purge & trap GC/MS is used to make measurements. The (10 min)
Drinking Water Test Method was revised in September Injection inlet temperature : 230˚C
2001 with the addition of a straightforward headspace Carrier gas : He 100kPa (high-pressure
GC/MS method to the conventional method. This page injection of 300kPa)
introduces considered results concerning the quantification Injection method : Total volume injection
aspect of this method.
MS
References Ionization : EI
Shimadzu Application News, No. M204 SIM monitor mass : 2-MIB (95, 107),
Drinking Water Test Method & Explanation Geosmin (112, 125)
(Fiscal 2001 Volume)
Japan Water Works Association
intensity intensity
(A) 2-MIB
6000
5500
10000
5000
4500
4000
3500
3000
2500 5000
2000
1500 95.00 95.00
1000 *1.00 *1.00
500 107.00 107.00
0 *1.00 0 *1.00
9 min 9 min
0.001µg/L 0.005µg/L
intensity intensity
(B) Geosmin
5000 15000
4500
4000
3500
10000
3000
2500
2000
1500 5000
112.00 112.00
1000 *1.00 *1.00
500 125.00 125.00
0 *1.00 *1.00
0
11 min 11 min
0.001µg/L 0.005µg/L
Fig. 12 SIM chromatogram
Area Area
[*10^4] [*10^4]
8 8 (B) Geosmin
(A) 2-MIB
r=0.9996 r=0.9997
5 5
[*10^1] [*10^1]
Conc. Conc.
Fig. 13 Calibration curve (0.001 to 0.050µg/L)
10
1.7 Analysis of Musty Smelling Components in Tap Water (SPME Method) - GC/MS
■Explanation not use organic solvents required by conventional solid-

Japanese tap water has established reputation in the area of phase extraction, and operation is simple and automation
safety as drinking water; however, musty smelling possible.
components in dam, lake and river surface water that is the The SPME-GC/MS method was used to measure odors and
source of tap water has become a summer problem, which the effectiveness reviewed. This page reports those results.
is being combated through the use of activated carbon. And References
the substances that cause this musty odor are 2- Shimadzu Application News, No. M209
methylisoborneol (2-MIB) and geosmin produced via blue- Drinking Water Test Method & Explanation (Fiscal 2001
green algae and actinomyces. The threshold value for the Volume)
odors is several ng/L, which is an extremely low Japan Water Works Association
concentration, so concentrating the sample in pretreatment
is important. In the Drinking Water Test Method, the solid- ■Analytical Conditions
phase extraction & GC/MS and purge & trap GC/MS had
SPME
been adapted as measurement methods. The Drinking
Water Test Method was revised in September 2001 with the SPME fiber : PDMS/DVB65µm
addition of a straightforward headspace GC/MS method Sample volume : 10mL + NaCl 3g
(Application News M204). Nevertheless, the extraction Sample temperature : 80˚C (30 min)
operation of the solid-phase extraction GC/MS method is GC
problematic in that it takes a lot of process time because the Column : DB-5
operation is cumbersome and a large amount of organic (30m ✕ 0.25mm I.D. df = 0.25µm)
solvent has to be used. Further, the purge & trap GC/MS Column temperature : 40˚C(3 min)-15˚C/min -250˚C (3min)
method requires an expensive system and machine Injection inlet temperature : 230˚C
maintenance is difficult. Carrier gas : He 100kPa
Whereas the solid-phase micro extraction method (SPME) Injection method : Splitless (3 min)
is a pretreatment method that can extract the organic
compound from the headspace of the liquid or solid sample, MS
concentrate it, apply thermal desorption in the vaporizing Ionization : EI
chamber of the gas chromatograph, and induct it into the SIM monitor mass : 2-MIB (95, 107),
column. This method is gathering attention because it does Geosmin (112, 125)
(1)2-MIB intensity intensity (2)Geosmin intensity intensity

geosmin
50000 400000 60000 600000

geosmin
45000 55000 550000

350000
50000 500000
40000
300000 45000 450000
35000
2-MIB
40000 400000
2-MIB
30000 250000
35000 350000
25000 200000 30000 300000
20000 25000 250000
150000
20000 200000
15000
100000 15000 150000
10000 95.00 95.00 112.00 112.00
*1.00 *1.00 10000 *1.00 100000 *1.00
5000 50000
107.00 107.00 5000 182.00 50000 182.00
0 *1.00 0 *1.00 0 *1.00 *1.00
0
11.0 11.1 11.2 11.3 11.4 11.5 11.0 11.1 11.2 11.3 11.4 11.5 14.5 14.6 14.7 14.8 14.9 15.0 14.5 14.6 14.7 14.8 14.9 15.0
min min min min
0.010µg/L 0.010µg/L 0.010µg/L 0.010µg/L
Fig. 14 SIM chromatograms
(1)2-MIB [*10^6] (2)Geosmin [*10^6]

ID#:1 m/z:95.00 Compound name:2-MIB ID#:2 m/z:112.00 Compound name:Geosmin
1 3
f(x)=22364490.302279*x+5991.570697 f(x)=64559563.075706*x-17585.304252
Correlation coefficient(R)=0.999499 Correlation coefficient(R)=0.999714
# Concentration (µg/L) Area # Concentration (µg/L) Area

1 0.001 26133 1 0.001 66289
2 0.010 246730 2 0.010 641253
3 0.020 434120 3 0.020 1224401
4 0.050 1128506 4 0.050 3227040
5 5
[*10^-2] [*10^-2]
Fig. 15 Calibration curves (0.001 to 0.050µg)
11
1.8 Analysis of Acrylamide in Water (1) - GC,GC/MS
■Explanation Reference
In 1974 the Environmental Sanitation Bureau of the Drinking Water Test Method & Explanation
Japanese Ministry of Health and Welfare prescribed that, as a (Fiscal 2001 Volume)
judgment criteria for well drinking water, acrylamide would be Japan Water Works Association
undetectable beyond the detection limit of 0.1ppm;
Lower Limit of Quantitationon
however, this prescription was abrogated in the water
0.02µg/L
quality standard established in December 1993.
Nevertheless, in March 2000, this issue was raised again as an ■Analytical Conditions
evaluation item in the test method guideline for evaluating tap Instrument : GC-17A (Ver. 3)
water chemicals by the waterworks office of the water Column : DB-WAX
supply & environmental sanitation department in the (30m ✕ 0.25mm I.D. df = 0.25µm)
Environmental Health Bureau of the Ministry of Health and Column temperature : 50˚C -10˚C/min -200˚C
Welfare. In the 1993 volume of the Drinking Water Test Injection inlet temperature : 250˚C
Method a packed-column analysis method was employed to Detector temperature : 250˚C (ECD-17)
analyze 2,3-Dibromopropionamide (2,3-DBPA) obtained Carrier gas : He 300kPa
through bromination of acrylamide; however, as 2,3-DBPA Injection method : Split (1:20)
was unstable, the following amendment was introduced to the Injection volume : 1µL
2001 volume.
The test method requires the bromination of acrylamide in test
water using potassium bromate in a situation where
bromide ions exist, followed by the extraction of the
synthesized 2,3-DBPA using ethyl acetate, and its
conversion to 2-Bromopropeneamide (2-BPA) using
triethylamine, so that a GC-ECD can measure it. Note that the
GC/MS method was added and employed in the 2001
volume.
0.0 0.0
2.0 2.0
4.0 4.0
6.0 6.0
8.0 8.0
10.0 10.0 Acrylamide Br

Position of acrylamide Br
12.0 12.0
14.0 14.0
Fig. 16 Chromatogram of sample extracted from tap water Fig. 17 Chromatogram of sample extracted from tap water with
acrylamide added (Equivalent to 0.1µg/L concentration in water)
12
1.8 Analysis of Acrylamide in Water (2) - GC,GC/MS

Negative chemical ionization (NCI) is effective in GC/MS GC
because of its selectivity and high sensitivity for halogen
Column : ZB-WAX (30m ✕ 0.25mm I.D.
compounds. This data introduces examples of analysis
df = 0.25µm)
using NCI-GC/MS.
Column temperature : 60˚C (2 min) -10˚C/min -200˚C (2 min)
References Injection inlet temperature : 200˚C
Shimadzu Application News, No. M199 Carrier gas : He 300kPa
Drinking Water Test Method & Explanation Injection method : Splitless (2.0 min)
(Fiscal 2001 Volume) Injection volume : 1µL
MS
Ionization : NCI (Isobutane)
Scan range : m/z 35 to 400
Monitored mass : 81, 79
Sample Sulfuric acid (1 +5) pH no more than 1
Derivatization Potassium bromate solution

Sodium thiosulfate solution
Solvent extraction Ethyl acetate O

Br O O
Dehydration Anhydrous sodium sulfate NH2 + Br2 – Br
NH2 NH2
Concentration
Br Br
Alkali addition Triethylamine
GC/NCI-MS
Fig. 18 Pretreatment flow Fig. 19 Derivatization reaction
Retension time: 15.8 (Scan #:216)

Retension time: 15.8 (Scan #:216) 4000000
100
79 3500000
3000000
2500000
2000000
15.795
1500000 TIC
*1.00
1000000 79.00
500000 *2.00
30 50 70 90 110 130 150 170 190 210 230 250 270 290 0
m/z
14 15 16 17 18
min
Fig. 20 NCI mass spectrum Fig. 21 NCI mass chromatogram for 0.5µg/L
79/81
ID#: 1 m/z: 79.00
Type: Target
Compound name: 2-Bromo proplyamide
150000 Retention time: 15.794
Area: 310069
5000000 TIC
100000 Concentration: 0.251µg/L
*1.00
79.00
15.800 *5.00
81.00 50000
*5.00 # m/z Area Measurement%
0 1 81.00 294742 95.00
14 15 16 17 18
min 0
15 16
Fig. 22 NCI chromatograms of acrylamide extracted from test water Fig. 23 Quantifying results for sample
13
1.9 Analysis of Golf Course Agrochemicals - GC/MS

In 1990 the Japanese Ministry of Health and Welfare and GC
the Environment Agency established substances, reference
Column : DB-1 (30m ✕ 0.32mm I.D. df
values and testing methods related to agrochemicals used at
= 0.25µm)
golf courses. Following on from this, standards for clean
Column temperature : 70˚C (2 min) -20˚C/min -150˚C
water, environment water and wastewater were tightened.
-3˚C/min -210˚C -10˚C/min -
The measuring method published by the Environment
300˚C (5 min)
Agency at the time was individual analysis using GC, etc.
Injection inlet temperature : 270˚C
However, in 1997, agrochemicals were added, so the test
Carrier gas : He 40kPa (2 min)
method was published as simultaneous analysis method
-2kPa/min -80kPa (16 min)
using GC/MS (some chemicals are tested using HPLC).
Injection method : Splitless (2.0 min)
This data introduces measuring examples using GC/MS
Injection volume : 1µL
mainly for the added agrochemicals acephate, metalaxyl,
dithiopyr and pyributicarb. MS
Ionization : EI
Reference
Scan range : m/z 35 to 400
Shimadzu Application News No. M188
Monitored mass : See Chart 2
Analysis Method I Analysis Method II Analysis Method III
200mL Sample 200mL Sample 200mL Sample
Adjust to pH 7 Adjust to pH 7
Solid-phase extraction Ethyl acetate extraction Concentrate & Desiccate by Nitrogen
Combine C18 column and activated carbon column, 10g NaCl
and flow sample through 50mL x 2 ethyl acetate 2mL constant volume (acetone)
Separate the two columns Dehydrate
Add 2% ethylene glycol GC/MS-GC-FPD
C18 Column Activated Carbon Column acetone solution Methamidophos
10mL acetone Eluation using 30mL of methanol Concentrate & Desiccate by Nitrogen
Elution using 5mL acetonitrile Add 2% ethylene glycol HPLC Analysis Method
Add 2% diethylene glycol acetone solution acetone solution
2mL constant volume (acetone) 250mL Sample
Concentrate & Desiccate by Nitrogen Concentrate & Desiccate by Nitrogen Adjust to pH 3.5
GC/MS-GC-ECD Solid-phase extraction
2mL constant volume (acetone) 2mL constant volume (acetone)
Etridiazole Polystyrene gel column
Chloroneb Eluation using 5mL acetonitrile
GC/MS GC/MS-GC-FPD Benfluralin Add 2% ethylene glycol acetone solution
25 components Acephate, trichlorfon Pyributicarb
Concentrate & Desiccate by Nitrogen
2mL constant volume (water & acetonitrile) ID Component SIM Atomic Mass Number
1 Pencycuron 180,109
HPLC
7 components
2 Simazine (CAT) 201,186
3 Diazinon oxone 273,137
Fig. 24 Pretreatment flow 4 Chlorothalonil (TPN) 266,264
5 Propyzamide 173,273
6 Diazinon 304,179
Data file name: Golf-C18.D10 7 MEP oxione 244,109
Sample: 28 components of new golf course agrochemical
Solid-phase extraction (C18) 10ppm 8 Triclorphos-methyl 265,267
TIC 6 8500000 9 Turbucarb (MBPMC) 220,205
10 Metalaxyl (addition) 206,160
9
2 11 Fenitrothion (MEP) 277,260
5
12 Dithiopyr (addition) 354,306
17
13 Chlorpyrifos 314,197
14 Captan 79,107,119
8
10
15 Pendimethalin 252,162
18 25 16 Methyldymuron 107,119
24 28
4
12
19 17 Isofenphos 213,255
3 13 22
18 Isopuothioram 290,162
1 21
11
19 Napropamide 271,128
27
15
20 Butamifos 286,200
16
7
14 21 Isoxathion oxione 105,161,254
20 23 26 22 Flutonil 323,173
23 Isoxathion 105,177,313
24 Triclopyrbutoxyethyl 210,212,182
25 Mepronil 119,269
26 Pyridaphenthion 340,199
27 Iprodione 314,316
28 Bensulide (SAP) 215,131
8 10 12 14 16 18 20 22 24 26 28
Fig. 25 Total ion chromatogram Chart 2 Monitor mass list
14
1.10 Analysis of Ethylenediamine Tetraacetic Acid (EDTA) - GC/MS
■Explanation References
In July 2001 the Japanese Drinking Water Test Method was Shimadzu Application News, No. M207
amended with the addition of a measuring method for Drinking Water Test Method & Explanation
ethylenediamine tetraacetic acid (EDTA). EDTA is widely (Fiscal 2001 Volume)
used in daily necessities including agricultural produce and Japan Water Works Association
food additives as well as being used in many industrial
goods, plating, pharmacy items and in the water softening ■Analytical Conditions
process, etc. Hardly any of the discharged EDTA GC
decomposes in the environment, and is thought to exist in Column : Solgel 1 (30m ✕ 0.25mm I.D.
the form of a metal chelate, which suggests that it is present df = 0.25µm)
in environment water, albeit in miniscule amounts. Column temperature : 60˚C (2 min) -15˚C/min -270˚C
Results of animal tests show that, although slender, EDTA (4 min)
is suspected of being toxic to mankind, which has led FAO Injection inlet temperature : 250˚C
and WHO to set a guideline value for EDTA to 0.6mg/L: an Carrier gas : He 100kPa
ADI of 1.9mg/kg of body weight/day allocating 1% to Injection method : Splitless (1.0 min/250kPa)
drinking water. While in the Drinking Water Test Method Injection volume : 1µL
for EDTA in water, the quantitative lower limit is set as
0.5µ g/L. Sample is concentrated 100 times in the MS
pretreatment operation, so the quantitative lower limit of Ionization : EI
0.05mg/L is met for the requirement of actually measuring Scan range : m/z 35 - 450
a test solution, which means that sensitivity is not a Monitored mass : EDTA 174, 289, 348
problem. Fig. 26 shows the analysis flow. CyDTA (IS) 343, 402
#: 1 Retention time: 15.4 (Scan #: 167)

100 174
100mL of sample water
45 146
IS (CyDTA 0.1mg/mL) 50µL
116 289
56 128 188 348
41 74 97
Vacuum concentrating to 2mL 157 208 235 264 275 296 316 350
30 50 70 90 110 130 150 170 190 210 230 250 270 290 310 330 350 m/z
50µL of formic acid
Desiccate by N2 gas Fig. 27 EDTA mass spectrum

15% BF3 - MeOH 1mL
Leave for 1hr at 80°C

#: 2 Retention time: 17.6 (Scan #: 436)
3mL phosphate buffer (pH 7) 100 168
1mL dichloromethane
Shaking & centrifuging

182 343
42 102 142 160 240 402
81 200 329
Dichloromethane liquid layer 41 128
67 96 112 213 228 254 269 283 297 311 370
GC/MS measuring 30 50 70 90 110 130 150 170 190 210 230 250 270 290 310 330 350 370 390 m/z
Fig. 28 CyDTA (IS) mass spectrum
Fig. 26 Pretreatment flow

SIM Chromatogram EDTA 20ppb-1
ETDA
IS(CyDTA)
5,437 174.10 176,159 402.15
O O 1,621 289.10
HO O O O
HO
239,873 343.15
N BF3 O N
N OH N O
OH
CH3OH 1,070 348.10
O O O
O
15.0 16.0 17.0 18.0 min
Fig. 29 Derivatization reaction Fig. 30 SIM chromatogram for 0.02mg/L standard sample
15
1.11 Analysis of Non-organic Components in Tap Water (1) - ICP-AES
With regard to the testing method for metals in tap water, A water sample of 100mL was prepared, 1mL of nitric acid
there are an analysis method using ICP emission added, and thermally concentrated without quite boiling.
spectroscopic method or atomic absorption method, and an Heating was stopped once solution volume dropped below
absorptiometric analysis as colorimetric method. Here, an 100mL, cooled, and measured up with purified water to
ICP emission spectroscopic analysis method as a create a 100mL sample for analysis.
simultaneous analysis method will be introduced.
Tap water was qualified and quantified using the ultrasonic ■Analytical Conditions
nebulizer in the ICP-AES. The results of the qualitative Instrument : ICPS-7500
analysis revealed Al, B, Ba, Ca, Cd, Cu, Fe, K, Mg, Mn, Ultrasonic nebulizer UAG-1
Na, S, Si, Sr, and Zn. Quantitative analysis was performed High-frequency : 27.12MHz
for the elements detected by qualitative analysis and the High-frequency output 0.8kW
:
elements laid down in the water quality standard. Cooling gas : Ar 14.0L/min
Plasma gas : Ar 1.2L/min
References Carrier gas : Ar 0.7L/min
(1) Partial amendment of Ministerial ordinance related to Purge gas : Ar 3.5L/min
water quality standard for drinking water and Water Sample suction rate : 2.0mL/min
Supply Law Operation Regulations, etc., introduced on Observation method : longitudinal
December 21, 1992
(2) Drinking Water Test Method & Explanation,
Japan Water Works Association volume
Element Analytical Value (mg/L) Element Analytical Value (mg/L) Element Analytical Value (mg/L)
A 0.0048 Cr <0.0005 Na 8.76
As <0.005 Cu 0.0005 Pb <0.002
B 0.025 Fe 0.0034 S 4.45
Ba 0.0052 K 1.36 Si 0.77
Ca 9.84 Mg 1.72 Sr 0.056
Cd 0.0003 Mn 0.0002 Zn 0.0022
Chart 3 Tap water analysis results (µg/mL)
16
1.11 Analysis of Non-organic Components in Tap Water (2) - ICP-AES
Fig. 31 Cd calibration curve
Fig.32 Al calibration curve
Fig. 33 Profile of Al 167.079nm Fig. 34 Profile of Cd 228.802nm Fig. 35 Profile of Cu 324.754nm
17
1.12 Analysis of Non-organic Components in Mineral Water (1) - ICP-AES
■Explanation References
Mineral water brands are forms of drinking water just like (1) Partial amendment of Ministerial ordinance related to
tap water, and large quantities of domestic and import water quality standard for drinking water and Water
brands are consumed, which has led to calls for Supply Law Operation Regulations, etc., introduced on
amendments of the regulations governing this type of water. December 21, 1992
The following is explanation of some highly sensitive (2) Partial amendment of operation ordinance for water
analysis performed to find traces of metal elements in pollution prevention related to environment standards,
mineral water using an ICP emission spectrometer and a introduced on March 8, 1993
Ultrasonic nebulizer.
One method of performing highly sensitive analysis ■Pretreatment
involves longitudinal observation of plasma. By using this Promptly transfer 50mL of sample to plastic beaker after
method, background spectrum is reduced by argon lighting, breaking seal on mineral water bottle, add 1mL of nitric
which enables highly sensitive measuring. As a result, acid, and stir sufficiently.
sensitivity can be improved by about 5 fold in comparison ■Analytical Conditions
with conventional lateral observation. Traces of metal Instrument : ICPS-7500
elements (Al, Cr, Mn, Fe, Mi, Cu, Zn, As, Se, Mo, Cd, Pb) Ultrasonic nebulizer UAG-1
were quantified using the ICP emission spectrometer and High-frequency : 27.12MHz
the Ultrasonic nebulizer. High-frequency output : 1.0kW
Some imported mineral water contain a large amounts of Cooling gas : Ar 14.0L/min
Ca (60 to 100 µg/mL) in comparison to domestic products. Plasma gas : Ar 1.2L/min
For this reason, background compensation is necessary for Carrier gas : Ar 0.8L/min
certain elements. Purge gas : Ar 3.5L/min
Sample suction rate : 2.0mL/min
Observation method : longitudinal
Sample A Sample B Sample C Sample D Sample E Sample F Sample G Sample H Sample I Qualitative Lower Limit
Al 0.46 <0.04 1.32 3.22 0.08 3.56 0.80 <0.04 <0.04 0.04
Cr <0.1 0.26 0.67 0.54 <0.1 <0.1 0.21 0.19 <0.1 0.1
Mn 0.10 0.19 0.07 <0.01 0.76 1.61 0.04 0.69 0.05 0.01
Fe <0.08 0.20 0.91 0.19 <0.08 <0.08 0.12 0.09 <0.08 0.08
Ni 0.37 0.31 0.93 0.18 0.36 0.60 0.57 0.34 <0.1 0.1
Cu 0.52 0.26 0.19 <0.1 <0.1 0.31 0.41 0.26 0.21 0.1
Zn 0.64 0.58 2.14 0.26 6.30 1.67 0.61 0.15 0.10 0.01
As <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 0.6
Se <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 <0.6 0.6
Mo <0.1 <0.1 <0.1 <0.1 1.52 3.22 2.02 0.46 <0.1 0.1
Cd <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 <0.02 0.02
Pb <0.4 <0.4 <0.4 <0.4 <0.4 <0.4 <0.4 <0.4 <0.4 0.4
Chart 4 Analysis results for mineral water (ng/mL)
18
1.12 Analysis of Non-organic Components in Mineral Water (2) - ICP-AES
Fig. 36 Pb calibration curve
Fig. 37 As calibration curve
Fig. 38 Peak profile of Mo Fig. 39 Peak profile of Cd Fig. 40 Peak profile of Pb
19
1.13 Direct Analysis of As in Tap Water and River Water - AA
■Explanation ■Sample Adjustments and Measuring Method

This data introduces a measuring example for As in tap 1mL of nitric acid per 100mL were added to tap water and
water and river water using the electro-thermal atomization river water, these were then heat treated, cooled, transferred
(furnace method) effective in measuring trace amounts of to measuring flasks, and filled with purified water to make
most elements. 100mL samples. Also, to check recovery, a reference
sample was prepared so that it had a concentration of 2ppb
■Quantification Limit after addition was made.
As: 0.2ppb Pd (as a matrix modifier) was added to provide 10ppm, and
the injection volume was set as 40µL.
Wavelength : 193.7nm
Slit : 1.0nm
Measuring mode : BGC-D2
Difference between
Temp program (Tube: pyro-coated graphite tube) Sample Measuring Result addition and non-addition Recovery
Stage Temp (°C) Time (sec) Heating mode Ar gas flow rate (L/min)
Tap water 0.063ppb
1.974ppb 98.7%
1 150 20 RAMP 0.10 Addition of tap water + 1ppb As 2.037ppb
2 250 20 RAMP 0.10
River water 0.138ppb
3 900 10 RAMP 1.00 2.034ppb 101.7%
4 900 10 STEP 1.00 Addition of river water + 1ppb As 2.172ppb
5 900 3 STEP 0.00
*6 2000 3 STEP 0.00
7 2300 2 STEP 1.00
*: Stage 6 is atomization stage
Chart 5 As measuring conditions Chart 6 As analysis results
Calibration curve (calibration curve #: 01) Tap water + 2ppb: SPIKE

0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200 0.225 0.250 0.275 0.300 0.325 0.350 0.375 0.400
Abs 0.200 Conc Abs 0.000
(ppb) 5.000
Set concentration Concentration Absorbance BG Actual concentration %R

0.150 2.0000 2.0384 0.0932 0.0038 2.0384 98.6869
0.5000 0.0194 0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200 0.225 0.250 0.275 0.300 0.325 0.350 0.375 0.400
0.000
0.100 1.0000 0.0424
5.000
0.050 2.0000 0.0905 Set concentration Concentration Absorbance BG

2.0000 2.0244 0.0925 0.0042
Actual concentration %R
2.0244 98.6869
4.0000 0.1845 0.000
0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200 0.225 0.250 0.275 0.300 0.325 0.350 0.375 0.400
0.000
0.000 1.000 2.000 3.000 4.000 5.000

Conc(ppb) 2.0000 2.0494 0.0937 0.0032 2.0494 98.6869
Tap water + 2ppb: SPIKE Average
Set concentration Concentration Absorbance BG Actual concentration Actual concentration unit %RSD SD %R
2.0000 2.0374 0.0931 0.0037 2.0374 ng/mL 0.6160 0.000574 98.6869
Abs=0.0457Conc+ 0
r=1.0000
Fig. 41 As calibration curve Fig. 42 Peak profiles at time of As analysis
20
1.14 Direct Analysis of Pb in Tap Water and River Water - AA
■Explanation ■Sample Adjustments and Measuring Method

This data introduces a measuring example for Pb in tap 1mL of nitric acid per 100mL were added to tap water and
water and river water using the electro-thermal atomization river water, these were then heat treated, cooled, transferred
(furnace method) effective in measuring trace amounts of to measuring flasks, and filled with purified water to make
most elements. 100mL samples. Also, to check recovery, a reference
sample was prepared so that it had a concentration of 1ppb
■Quantification Limit after addition was made.
Pb: 0.1ppb Pd (as a matrix modifier) was added to provide 10ppm, and
the injection volume was set as 40µL.
Wavelength : 283.3nm
Slit : 1.0nm
Measuring mode : BGC-D2
Difference between
Temp program (Tube: pyro-coated graphite tube) Sample Measuring Result addition and non-addition Recovery
Stage Temp (°C) Time (sec) Heating mode Ar gas flow rate (L/min) Tap water 0.040ppb
0.977ppb 97.7%
1 150 20 RAMP 0.10 Addition of tap water + 1ppb Pb 1.017ppb
2 250 20 RAMP 0.10 0.521ppb
River water
3 800 10 RAMP 1.00 0.991ppb 99.1%
Addition of river water + 1ppb Pb 1.512ppb
4 800 10 STEP 1.00
5 800 3 STEP 0.00
*6 2000 3 STEP 0.00
7 2400 2 STEP 1.00
*: Stage 6 is atomization stage
Chart 7 Pb measuring conditions Chart 8 Pb analysis results
River water without addition: UNK

0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200
0.000
4.000
Concentration Absorbance BG Actual concentration

0.5420 0.0188 0.0024 0.5420
0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200
0.000
4.000
Calibration curve (calibration curve #: 01) Concentration Absorbance BG

0.5200 0.0180 0.0018
Actual concentration
0.5200
0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200
Abs 0.075 Conc Abs 0.000
(ppb) 4.000
Concentration Absorbance BG Actual concentration

0.050 0.1000 0.0034 0.4997 0.0173 0.0021 0.4997
River water without addition: UNK Average
0.2000 0.0068 Concentration Absorbance BG
0.5206 0.0180 0.0021
Actual concentration Actual concentration unit %RSD
0.5206 ng/mL 4.0678
SD
0.000733
0.025
0.5000 0.0175
0.000
1.0000 0.0339
River water + 1ppb: SPIKE
0.000 0.500 1.000 1.500 2.000

2.0000 0.0695 0.000
0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200
Conc(ppb) 4.000
1.0000 1.5343 0.0531 0.0030 1.5343 99.1492
0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200
0.000
Abs=0.0346Conc+ 0
4.000
r=0.9999 Set concentration Concentration Absorbance BG

1.0000 1.4885 0.0515 0.0028
Actual concentration %R
1.4885 99.1492
0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200
0.000
4.000
1.0000 1.5145 0.0524 0.0028 1.5145 99.1492
River water + 1ppb: SPIKE Average
Set concentration Concentration Absorbance BG Actual concentration Actual concentration unit %RSD SD %R
1.0000 1.5124 0.0523 0.0029 1.5124 ng/mL 1.5209 0.000796 99.1492
Fig. 43 Pb calibration curve Fig. 44 Peak profiles at time of Pb analysis
21
2. Environment Water
2.1 Analysis of Anions in River Water (1) - Ion Chromatograph
River and lake water – which is the source of our daily tap Filtering through a membrane filter (0.45µ m) for ion
water – needs to be constantly analyzed and monitored, as chromatography
any change in the water quality can directly affect human
health. Furthermore, the inorganic anion components in ■Analytical Conditions
river and lake water reflect the nature of the water source Instrument : Ion chromatograph (suppressor system)
and soil, so that each variation in ion concentration can be Column : Shim-pack IC-SA2
used to indicate change in the environment. Also, in recent (250mm ✕ 4.0mm I.D.)
years, eutrophication problems are occurring in rivers and Mobile phase : 12mM sodium hydrogen carbonate
lakes due to the inflow of domestic wastewater. And, once (NaHCO3)
again, the analysis of inorganic ions is important for 0.6mM sodium carbonate (Na2CO3)
research work on the causes and levels of pollution. Flow rate : 1.0mL/min
Temperature : 30˚C
References Detection : Electric conductivity detector
Drinking Water Test Method & Explanation (Fiscal 2001
Volume)
Component Concentration Unit

–
1 F 0.067 ppm
–
2 Cl 8.003 ppm
–
20 2 0.25 3 NO2 0.047 ppm

–
4 Br 0.022 ppm
3
µS/cm
–
4 5 NO3 3.399 ppm
2–
6 SO4 9.980 ppm
15 2 5
µS/cm
6 8 min
10
5
5
1 3
0
0 5 10 15 min
Fig. 45
22
Environment Water
2.1 Analysis of Anions in River Water (2) - Ion Chromatograph

Filtering through a membrane filter (0.45 µ m) for ion Instrument : Ion chromatograph
chromatography Column : Shim-pack IC-A3 (150mm ✕ 4.6mm I.D.)
Mobile phase : 8.0mM p-hydroxybenzoic acid, 3.2mM
Bis-Tris*
Temperature : 40˚C
*Bis-Tris : Bis (2-hydroxyethyl) iminotris
■Peaks ■Peaks
–
1 CO32– 1 CO32
–
2 F– (0.088mg/L) 2 PO43 (0.106mg/L)
–
3 Cl– (6.10mg/L) 3 F (0.148mg/L)
–
4 NO2– (0.048mg/L) 4 Cl (10.19mg/L)
–
5 Br– (0.21mg/L) 5 NO2 (0.138mg/L)
–
6 NO3– (1.28mg/L) 6 Br (0.019mg/L)
–
7 SO42– (7.78mg/L) 7 NO3 (2.55mg/L)
2–
8 SO4 (15.73mg/L)
Fig. 46 Analysis of river water A Fig. 47 Analysis of river water B
23
2.2 Analysis of Cations in River Water (1) - Ion Chromatograph

chromatography (non-suppressor system)
Column : Shim-pack IC-SC1
(150mm ✕ 4.6mm I.D.)
Mobile phase : 3.0mM sulfuric acid
Temperature : 30˚C
Component Concentration Unit

+
1 Li 0.049 ppm
+
2 Na 13.719 ppm
+
30 3 NH4 0.041 ppm
+
4 K 2.745 ppm
2 5 Mg2
+
4.081 ppm
+
6 Ca2 23.167 ppm
20
µS/cm
10 6
5
4
1 3
0
0 5 10
Analysis of river water C
24
Environment Water
2.2 Analysis of Cations in River Water (2) - Ion Chromatograph
■Pretreatment ■Analytical Conditions(Fig. 50)

Filtering through a membrane filter (0.45 µ m) for ion Instruement : Ion chromatograph
chromatography Column : Shim-pack IC-C3 (100mm ✕ 4.6mm I.D.)
Mobile phase: 1.0mM Dipicolinic acid
■Analytical Conditions(Fig. 49) 1.0mM oxalic acid
Instruement : Ion chromatograph Flow rate : 1.2mL/min
Column : Shim-pack IC-C3 (100mm ✕ 4.6mm I.D.) Temperature : 40˚C
Mobile phase: 2.5mM oxalic acid Detection : Electric conductivity detector
Temperature : 40˚C
■Peaks ■Peaks
+ +
1 Na (12.42mg/L) 1 Li (0.007mg/L)
+ +
2 K (2.73mg/L) 2 Na (19.63mg/L)
+ +
3 Mg2 (4.38mg/L) 3 NH4 (0.106mg/L)
+ +
4 Ca2 (16.93mg/L) 4 K (4.09mg/L)
+
5 Ca2 (21.63mg/L)
2+
6 Mg (4.13mg/L)
Fig. 49 Analysis of river water A Fig. 50 Analysis of river water B
25
2.3 Analysis of Anions in Lake Water - Ion Chromatograph
The river and lake water – which is the source of our daily Filtering through a membrane filter (0.45 µ m) for ion
tap water – needs to be constantly analyzed and monitored chromatography
as any change in the water quality can directly affect human
health. Furthermore, the non-organic negative ion ■Analytical Conditions
components in river and lake water reflect the nature of the Instrument : Ion chromatograph
water source and soil, so that each variation in ion Column : Shim-pack IC-A3 (150mm ✕ 4.6mm I.D.)
concentration can be used to indicate change in the Mobile phase : 8.0mM p-hydroxybenzoic acid, 3.2mM
environment. Also, in recent years, eutrophication problems Bis-Tris*
are occurring in rivers and lakes due to the inflow of Flow rate : 1.5mL/min
domestic wastewater, which makes the analysis of non- Temperature : 40˚C
organic ions even more important for research work on the Detection : Electric conductivity detector
causes and levels of pollution. *Bis-Tris : Bis (2-hydroxyethyl) iminotris
References
Drinking Water Test Method & Explanation (Fiscal 2001
Volume)
■Peaks
–
1 CO32
–
2 F (0.147mg/L)
–
3 Cl (9.65mg/L)
–
4 NO2 (0.059mg/L)
–
5 Br (0.030mg/L)
–
6 NO3 (0.309mg/L)
–
7 SO42 (12.38mg/L)
Fig. 51 Analysis of lake water A
26
Environment Water
2.4 Analysis of Cations in Lake Water - Ion Chromatograph

chromatography Column : Shim-pack IC-C3 (100mm ✕ 4.6mm
I.D.)
Temperature : 40˚C
■Peaks
+
1 Na (12.42mg/L)
+
2 K (2.73mg/L)
+
3 Mg2 (4.38mg/L)
2+
4 Ca (16.93mg/L)
Fig. 52 Analysis of lake water B
27
2.5 Analysis of Anions in River Water - PIA-1000

This is a river-water analysis example using the personal Instrument : PIA-1000
ion analyzer PIA-1000. In this kind of example, the PIA- Column : Shim-pack IC-A3(S)
1000 is a potent force as it can be taken directly to an (150mm ✕ 2.0mm I.D.)
analyzing site. Mobile phase : PIA-1000 dedicated anion analysis mobile
phase, IC-MA3-1
■Pretreatment Flow rate : 0.2mL/min
Filtering through a membrane filter (0.45 µ m) for ion Temperature : 35˚C
chromatography
■Peaks
–
1 HCO3 (52.77mg/L)
3–
2 PO4 (0.235mg/L)
–
3 F (0.076mg/L)
–
4 Cl (15.72mg/L)
–
5 NO3 (7.44mg/L)
2–
6 SO4 (15.04mg/L)
Fig. 53 Analysis example of river water (PIA-1000)
28
Environment Water
2.6 Analysis of Cations in River Water - PIA-1000

Filtering through a membrane filter (0.45 µ m) for ion Instrument : PIA-1000
chromatography Column : Shim-pack IC-C3(S)
(100mm ✕ 2.0mm I.D.)
Mobile phase : PIA-1000 dedicated cation analysis mobile
phase, IC-MC3-1
Temperature : 35˚C
■Peaks
+
1 Na (13.33mg/L)
+
2 NH4 (0.396mg/L)
+
3 K (2.786mg/L)
+
4 Mg2 (4.336mg/L)
2+
5 Ca (17.07mg/L)
Fig. 54 Analysis example of river water (PIA-1000)
29
2.7 Analysis of Calcium and Magnesium in River Water - AA
■Explanation ■Sample Adjustments

The atomic absorption method is one of the widely used Sample adjusting is shown in figure 58. In the case of
analysis methods for analyzing chemical elements in calcium and magnesium analysis, an equal amount of
solutions because of its simplicity and speed. Here is an lanthanum is added to the total sample including the
analysis example for Ca and Mg in standard substances in standard solution to mask interference by coexisting
river water currently on the market. elements.
■Analytical Conditions
References Instrument : AA-6200
Water test method for factories (JIS K0101) Analysis wavelength : Ca 422.7nm
: Mg 285.2nm
Quantitative lower limit value (target) Flame type : air acetylene
Ca : 0.09mg/L Background compensation : D2 method
Mg: 0.004mg/L Interference control agent : La 0.2%w/v
Overwriting Mg:0.20mg/L
Mg:0.10mg/L
Mg:0.04mg/L
Fig. 56 Mg signal profile
Fig. 55 Ca calibration curve A Take all of the appropriate sample in a 100mL measuring flask
➔
Add 2mL of hydrochloric acid (1 + 1)
➔
Add 4mL of lanthanum solution (5%w/v)
Add water up to the mark
Measure using flame atomic absorption method
Fig. 58 Sample adjustment
Fig. 57 Mg calibration curve

Remarks
Ca Mg If there is suspended matter in the sample, remove it by filtering or
SLRS-3 6.02(6.0±0.4) 1.60(1.6±0.2) use of a centrifuge. Calcium coexists with orthophosphate, sulfate
NIST1643d 31.2(31.04±0.50) 7.97(7.989±0.035) and aluminum, etc., while magnesium coexists with aluminum, so
both are impeded. This interference can be removed by adding
Chart 9 Measuring results Unit: mg/L lanthanum to mask out the coexisting elements. Add lanthanum to
Certified value in parenthesis sample in equal amounts to the standard solution.
30
Environment Water
2.8 Analysis of Total Nitrogen and Total phosphorus in River Water - UV
■Explanation ■Measuring Instrument

The remarkable overgrowth of plant plankton in sea areas High pressure boiling instrument sterilizer : KT2-2322
and rivers known as red water or red tide is said to be Spectrophotometer: : UV-1600 PC
linked to concentrations of nitrogen and phosphorus. Due to
rises in the concentration (eutrophication) of these,
environment standards and effluent standards have been
laid down by the Environment Agency. Here, the total
nitrogen and total phosphorus in the water of a river were
measured using the method laid down in the factory
wastewater test method (JIS K0102).
References
JIS K0102 Factory wastewater test method
Standard Sample Concentration (ppm) Absorbance Standard Sample Concentration (ppm) Absorbance
1 0.0000 0.000 1 0.0000 0.000
2 1.0000 0.205 2 0.5000 0.340
3 5.0000 1.023 3 1.0000 0.696
Chart 10 Standard sample measuring results A for total nitrogen Chart 11 Standard sample measuring results B for total phosphorus
Absorbance Calibration curve Calibration curve

Absorbance
1.2
0.7
1
0.6
0.8 0.5
0.6 0.4
0.4 0.3
0.2
0.2
0.1
0 0
0 1 2 3 4 5 6 0 0.5 1
Concentration (ppm) Concentration (ppm)
Fig. 59 Calibration curve for total nitrogen Fig. 60 Calibration curve for total phosphorus
Sample No. Concentration (ppm) Absorbance Sample No. Concentration (ppm) Absorbance
1 0.431 0.088 1 0.0138 0.007
2 0.563 0.115 2 0.0167 0.009
3 0.504 0.103 3 0.181 0.124
4 1.042 0.213 4 0.179 0.122
5 0.884 0.181 5 0.671 0.465
6 0.892 0.183 6 0.692 0.479
7 0.892 0.183 7 0.177 0.121
8 5.115 1.047 8 0.179 0.122
Chart 12 Total nitrogen measuring results A Chart 13 Total phosphorus measuring results B
31
2.9 Direct Analysis of Cd and Cr in Seawater - AA
■Explanation ■Sample Adjustments

The electro-thermal atomization (furnace method) can After filtering collected seawater, the standard liquid was
directly measure even complicated matrix samples. Here, added to obtain samples with 2ppb of Cd and 2.5ppb of Cr.
the data introduces a measuring example using a standard Next, 1mL of nitric acid per 100mL of sample was added,
addition method for samples made up of seawater to which heat treated, cooled, transferred to a measuring flasks, and
constant amounts of cadmium and chrome have been filled with purified water to make 100mL samples.
added.
■Quantification Limit
Cd: 0.5ppb (diluted 10 times, concentration in original sample)
Cr: 0.3ppb (diluted 5 times, concentration in original sample)
Monochromator Parameters Monochromator Parameters

Element : Cd Element : Cr
Wavelength : 228.8nm Wavelength : 357.9nm
Slit width : 1.0nm Slit width : 1.0nm
Current : 8 mA Current : 10 mA
Lighting mode : BGC-D2 Lighting mode : BGC-D2
Temp Program Temp Program
Ashing : 20sec at 600°C Ashing : 30sec at 1300°C
Atomization : 5sec at 1000°C Atomization : 2sec at 2300°C
Tube : High-density graphite tube Tube : pyro-coated graphite tube
Injection volume : 2µL Injection volume : 4µL
Total injection volume: 20µL Total injection volume: 20µL
Modifier: Addition of 4µL of palladium nitrate 200ppm solution Modifier: Addition of 4µL of palladium nitrate 200ppm solution
Peak Profiles Peak Profiles
0.500 0.500
0.400 0.400
0.300 0.300
0.200 0.200
0.100 0.100
0.000 0.000
Sample Blank Without additive +0.2ppb +0.4ppb +0.6ppb Sample Blank Without additive +0.5ppb +1ppb +1.5ppb
Absorbance 0.0052 0.0356 0.0757 0.1137 0.1484 Absorbance 0.0178 0.0751 0.1461 0.2235 0.2888
Calibration Curve for Standard Addition Method Calibration Curve for Standard Addition Method
A 0.150 A 0.300
b Sample
b
s s 0.250 Absorbance
0.100 0.200
0.150
0.050 0.100
0.050
0.000 0.000
0.000 0.500 0.000 1.000
Conc(ppb) Conc(ppb)
Analysis Results Analysis Results
Measured value 0.196ppb Measured value 0.526ppb

Concentration in seawater 1.96ppb Concentration in seawater 2.63ppb
Additive concentration 2ppb Additive concentration 2.5ppb
Recovery 98% Recovery 105%
Fig. 61 Measurement of Cd in seawater Fig. 62 Measurement of Cr in seawater
32
Environment Water
2.10 Analysis of Non-organic Components in River Water (1) - ICP-MS
The testing methods of the Environment Standard item Nitric acid was added to 50mL of sample, boiled for
have been amended, so that the ICP mass spectrometry approximately 10 minutes over a hot plate, cooled,
(ICP-MS) method has been adopted for analysis of non- measured up to 50mL with ultra purified water, and stirred
organic metal elements. ICP-MS is noted for the feature of thoroughly.
being able to handle many of the chemical elements with a
technique that simultaneously analyzes with high ■Analytical Conditions
Instrument : ICPM-8500
sensitivity. Here, an example of river water analysis using
High-frequency : 27.12MHz
the inductively coupled plasma mass spectrometer ICPM-
High-frequency output : 1.2kW
8500 will be introduced. As river water is a source of tap
Cooling gas : Ar 7.0L/min
water, it is one of the most commonly tested and important
Plasma gas : Ar 1.5L/min
samples among environment samples. In this test,
Carrier gas : Ar 0.7L/min
quantitative analysis of standard substances in river water
Sample induction unit : Coaxial nebulizer/water cooling
JAC0031 and JAC0032 (Japan Society for Analytical
chamber (5˚C)
Chemistry Approval) was performed.
Sample suction rate : 0.4mL/min
Ion induction system : Pt type sampling cone
References : Pt type skimmer cone
(1) Partial amendment of Ministerial ordinance related to
water quality standard for drinking water and Water
Supply Law Operation Regulations, etc., introduced on
December 21, 1992
(2) Revision of Water Quality Pollution Prevention Law,
etc, introduced on March 8, 1993
River Water Standards JAC 0031 (without addition) River Water Standards JAC 0032 (added)
Element Mass Number Detection Limits
Measured Value Guaranteed Value Recovery (%) Measured Value Guaranteed Value Recovery (%)
B 11 8.6 95 57.8 98 0.004
Al 27 13.4 100 62.7 103 0.002
Cr 52 0.16 111 10.1 100 0.006
Mn 55 0.43 93 5.4 100 0.003
Ni 60 0.2 - 10.1 99 0.003
Cu 63 0.86 98 10.2 97 0.003
Zn 66 0.74 94 10.9 96 0.001
As 75 0.27 98 5.7 104 0.005
Se 77 0.13 - 5.2 100 0.03
Cd 114 0.005 - 1.06 106 0.001
Pb 208 0.029 112 10.3 104 0.001
Unit: ng/mL
Chart 14 River water analysis results (ng/mL) ( ): Referencial value
33
2.10 Analysis of Non-organic Components in River Water (2) - ICP-MS
Fig. 63 Pb calibration curve
Fig. 64 Cd calibration curve
Fig. 65 Pb 208 mass spectra Fig. 66 Cd 114 mass spectra Fig. 67 Cr 52 mass spectra
34
Environment Water
2.11 Analysis of Anions in Hot Spring Water - Ion Chromatograph

This shows an analysis example for non-organic anions and Column : Shim-pack IC-A1 (100mm ✕ 4.6mm I.D.)
cations in hot spring water. Mobile phase : 6.0mM boric acid
1.8mM mannitol
■Pretreatment 7. 5mM Tris (hydroxymethyl)
Filtering through a membrane filter (0.45 µ m) for ion aminomethane (pH 7.9)
chromatography Flow rate : 1.5mL/min
Temperature : 40˚C
■Peaks
–
1 HCO3
–
2 Cl
–
3 NO3
2–
4 SO4
Fig. 68 Analysis of hot spring water
35
2.12 Analysis of Cations in Hot Spring Water (1) - Ion Chromatograph

Filtering through a membrane filter (0.45 µ m) for ion Column : Shim-pack IC-C1 (150mm ✕ 5.0mm I.D.)
chromatography Mobile phase : 5mM of nitric acid
Temperature : 40˚C
■Peaks
+
1 Na
+
2 NH4
+
3 K
Fig. 69 Hot spring water
36
Environment Water
2.12 Analysis of Cations in Hot Spring Water (2) - Ion Chromatograph

Filtering through a membrane filter (0.45 µ m) for ion Column : Shim-pack IC-C1 (150mm ✕ 4.6mm I.D.)
chromatography Mobile phase : 4mM of tartaric acid, 2mM ethylenediamine
Temperature : 40˚C
■Peaks
+
1 Mg2
+
2 Ca2
Fig. 70 Hot spring water
37
2.13 Analysis of Anions in Rainwater - Ion Chromatograph
In recent years, the acidification of rainfall has progressed, Filtering through a membrane filter (0.45 µ m) for ion
and is adversely affecting ecosystems. The main cause of chromatography
acid rain is thought to be that SOx and Nox converts to
H2SO4, HNO3, etc., in Rainwater. The pH level in Rainwater ■Analytical Conditions
is set as the criteria for acid rain; however, as pH is Instrument : Ion chromatograph
standardized from the equivalent weight relationship of Column : Shim-pack IC-A3 (150mm ✕ 4.6mm I.D.)
acidic elements and alkali elements, the detailed causes and Mobile phase : 8.0mM p-hydroxybenzoic acid,
affects of acid rain cannot be fully determined from the pH 3.2mM Bis-Tris*
value alone. As shown in chart 15, the Environment Flow rate : 1.5mL/min
Agency have designated 8 elements as analysis items. An Temperature : 40˚C
ion chromatograph – which can handle simultaneous Detection : Electric conductivity detector
multiple ion analysis - is suitable for the analysis of these *Bis-Tris : Bis (2-hydroxyethyl) iminotris
items. (hydroxymethyl) methane
Sample Amt Conc Allowed ■Peaks

Ion –
1 Cl (64.1µg/L)
–
2 NO2 (21.1µg/L)
SO4 2- 2 0.06 –
3 NO3 (827.8µg/L)
NO3 - 2 0.05 2–
4 SO4 (739.6µg/L)
CI - 2 0.01
Na+ 2 0.03
NH4+ 2 0.02
K+ 2 0.02
Mg2+ 2 0.01
Ca2+ 2 0.02
Chart 15 Rainwater element analysis items in environment agency studies
Fig. 71 Rainwater
38
Environment Water
2.14 Analysis of Cations in Rainwater - Ion Chromatograph
■Pretreatment
Filtering through a membrane filter (0.45 µm) for ion
chromatography
Instrument : Ion chromatograph
Column : Shim-pack IC-C3 (100mm ✕ 4.6mm I.D.)
Temperature : 40˚C
■Peaks
+
1 Na (420µg/L)
+
2 NH4 (139µg/L)
+
3 K (554µg/L)
+
4 Mg2 (158µg/L)
2+
5 Ca (178µg/L)
Fig. 72 Analysis of rainwater
39
2.15 Analysis of Anions in Rainwater - PIA-1000
This is an example of Rainwater analysis using the personal Filtering through a membrane filter (0.45 µ m) for ion
ion analyzer PIA-1000. chromatography
Instrument : PIA-1000
Column : Shim-pack IC-A3(S) (150mm ✕ 2.0mm I.D.)
Mobile phase : PIA-1000 dedicated negative ion analysis
mobile phase, IC-MA3-1
■Peaks
–
1 F (0.043mg/L)
–
2 Cl (17.93mg/L)
–
3 Br (0.067mg/L)
–
4 NO3 (2.440mg/L)
–
5 SO42 (7.715mg/L)
Fig. 73 Rainwater
40
Environment Water
2.16 Analysis of Cations in Rainwater - PIA-1000

This is an example of rainwater analysis using the personal Instrument : PIA-1000
ion analyzer PIA-1000. Column : Shim-pack IC-C3(S) (100mm ✕ 2.0mm I.D.)
Mobile phase : PIA-1000 dedicated positive ion analysis
■Pretreatment mobile phase, IC-MC3-1
Filtering through a membrane filter (0.45 µ m) for ion Flow rate : 0.2mL/min
chromatography Temperature : 35˚C
■Peaks
+
1 Na (9.673mg/L)
+
2 NH4 (0.607mg/L)
+
3 K (0.638mg/L)
+
4 Mg (1.196mg/L)
+
5 Ca2 (1.294mg/L)
Fig. 74 Rainwater
41
2.17 Analysis of Sulfurous Acid Ions in Rainwater - HPLC

Sulfurous acid is contained in factory exhaust and vehicle Instrument : LC-VP system
exhaust, and is one of the substances that cause acid rain.
The Rankine method and ion chromatograph method are (Separation Conditions)
known as quantitative analysis methods for sulfurous acid; Column : Shim-pack IC-A1 (100mm ✕
however, from the point of view of operability, sensitivity 4.6mm I.D.)
and measuring accuracy, both methods have problems. Mobile phase : 10mM of citric acid
Here, a newly developed derivatizing fluorometric detector (ammonium) buffer solution
is introduced as an alternative. (pH 3.2)
With this method, the sulfurous acid is made to react with Flow speed : 1.0mL/min
formaldehyde, induced into a stable hydroxy Temperature : 50˚C
methansulfonic acid, and decomposition controlled through
the sample processing time and separation process. After (Detection Conditions)
separation, the sample is made to react with the existing Reaction reagent : (A) 10mM of methanol containing
orthophthalaldehyde (OPA) and primary amine, induced orthophthalaldehyde
into an isoindole derivative, and the target element (B) 500mM boric acid (sodium)
fluorescently detected. As a result, unstable sulfurous acid buffer solution (pH 9.2)
compounds can be quantitatively analyzed at a high level of (A)/(B) = 1/4 (v/v)
accuracy and high sensitivity. Reaction reagent flow rate : 0.5mL/min
Temperature : 50˚C
■Pretreatment Detection : fluorometric detector Ex = 320nm
Add citric acid (sodium) (10 mM) containing formaldehyde Em = 390nm
(10 mM) buffer solution (pH 4.4) to an equal amount of
rainwater sample immediately after it has been collected,
stir well, let it stand for a minute, then inject.
Reference
Masatoshi Takahashi, Masayuki Nishimura, Morimasa
Hayashi, Shimadzu Review Vol. 54, No. 4 (1997)
1 3
■Peaks
–
1 SO32 (210pmol/ml)
9 8
4
2
10 6 5
1,2: pumps,3: injector, 4: column oven,

5: fluorescence detector, 6: data processor, 7: reactor,
8: column, 9:mobile phase, 10: reagent.
Fig. 75 Instrument configuration Fig. 76 Rainwater
42
Environment Water
2.18 Analysis of Anions in Snow Water - Ion Chromatograph
Snow water shows acidification tendencies similar to Filtering through a membrane filter (0.45 µ m) for ion
Rainwater, and is having an adverse affect on ecosystems. chromatography
In recent years, there have been reports stating that snow
crystals have deformed into T-shaped and bar-shaped ■Analytical Conditions
crystals due to sulfur oxide in exhaust smoke and exhaust Instrument : Ion chromatograph
gas. This comes about from foreign matter in the Column : Shim-pack IC-A1 (100mm ✕ 4.6mm I.D.)
atmosphere acidifying snow, which hinders the formation Mobile phase : 2.5mM of phthalic acid, 2.4mM of Tris
of snow crystals causing them to become deformed. This (hydroxymethyl) aminomethane (pH 4.0)
phenomenon has tended to increase from 1993 onward. Flow rate : 1.5mL/min
Temperature : 40˚C
■Peaks ■Peaks
– –
1 Cl 1 Cl
– –
2 NO3 2 NO3
2– 2–
3 SO4 3 SO4
Fig. 77 Analysis of snow water Fig. 78 Analysis of snow water
43
2.19 Analysis of Anions in Sea Water - HPLC
Nitrogen atoms in seawater are said to exist as ions of Filtering through a membrane filter (0.45 µ m) for ion
which nearly all are composed from either NO2–, NO3–, or chromatography
NH 4 + . Ion chromatography is well configured as
identification analysis method for nitrogen in seawater as it ■Analytical Conditions
is able to quantify each of the above ions separately. Instrument : LC-VP system
However, conventional ion chromatography using electric Column : Asahipak NH2P-50 (250mm ✕ 4.6mm
conductivity detection has problems accurately quantifying I.D.)
these ions because of the influence of sodium and chloride Mobile phase : 10mM of phosphoric acid (sodium) buffer
ions, which exists in vast amounts in seawater. NO2– and solution (pH 6.9)
NO3– absorb comparatively well in the ultraviolet region, containing 150mM of sodium perchlorate
whereas the ions of Cl– and SO42–, etc., are hardly able to Flow rate : 0.8mL/min
absorb any ultraviolet, so an ultraviolet absorption detection Temperature : 35˚C
method is a well-suited method for analyzing NO 2– and Detection : UV-VIS detector 214nm
NO3–. In this case, phosphoric acid buffer solution, which
has little ultraviolet absorption is used as the mobile phase
for analysis, and detection is conducted at the 210nm level.
Also, under these conditions, bromide ions can be analyzed
at high accuracy.
■Peaks
–
1 NO2
–
2 Br
–
3 NO3
Fig. 79 Seawater
44
Environment Water
2.20 Analysis of Ammonia Ions in Sea Water - HPLC

NH 4+ reacts with orthophthalaldehyde (OPA) to form Instrument : LC-VP system
fluorescent chromaphore. When this reaction is applied to Column : Shim-pack ISC-07/S1504Na
analysis of seawater, the various ions that coexist do not (150mm ✕ 4.0mm I.D.)
influence analysis, thus enabling highly accurate Trap column : Shim-pack ISC-30/S1504Na
quantifying of NH4+. The following is an example of NH4+ (50mm ✕ 4.0mm I.D.)
analyzed in seawater using an amino acid analysis system. Mobile phase : 0.60 N of sodium citrate, 0.20 M of
boric acid (pH 10.0, adjusted with
■Pretreatment NaOH solution)
Filtering through a membrane filter (0.45 µ m) for ion Flow rate : 0.3mL/min
chromatography Temperature : 55˚C
Reaction reagent : OPA solution
Reaction reagent flow rate : 0.3mL/min
Detection : Fluorometric detector Ex = 348nm
Em = 450nm
■Peaks
+
1 NH4
Fig. 80 Seawater
45
2.21 Analysis of Fluoride Ions in Sea Water (1) - Ion Chromatograph
When analyzing fluoride ions with an ion chromatograph, See next item for details.
chloride ions - that are amply contained in seawater -
interfere with analysis, and prior selective removal of these ■Analytical Conditions
chlorine ions is required using a silver-type cation Instrument : Ion chromatograph
replacement cartridge. However, this method causes a drop Column : Shim-pack IC-A3 (150mm ✕ 4.6mm
in the collection rate, and accurate analysis cannot be I.D.)
performed. Here, the diffusive separation method is Mobile phase : 8.0mM p-hydroxybenzoic acid, 3.2mM
effective in resolving this problem. A combination of the Bis-Tris*
diffusive separation method and ion chromatography was Flow rate : 1.5mL/min
investigated by professor Okutani et al of the Nihon Temperature : 40˚C
University, and it was found that Shim-pack IC-A3 column Detection : Electric conductivity detector
has the most suitable features for this method, so now *Bis-Tris : Bis (2-hydroxyethyl) iminotris
fluorine ions of 1 ppm or less in seawater can be measured (hydroxymethyl) methane
with high accuracy.
■Peaks
1 F – (1.15mg/L)
Fig. 81 Fluoride ions in seawater
46
Environment Water
2.21 Analysis of Fluoride Ions in Sea Water (2) - Ion Chromatograph
Reference Example 1
(Diffusive Separation Method)
Diffusive separation uses an acrylic resin diffusion 2.7NHClO4), the inner box (C compartment) is filled with
container configured of a box within a box, with the inner 10mL of absorption solution (0.1N NaOH). After sealing
box being able to divide the outer box when the whole the lid on the container, the sample and reaction solution of
container is tilted on its side. The diagrams on the right the outer box are mixed, and left to stand for a night so that
depict the diffusion container from overhead and side view. the fluoride ions will be quantitatively absorbed into the
When diffusion is actually performed, first the outer box absorption solution. As the absorption solution has strong
compartments (A and B) divided by the inner box are alkalinity, it is neutralized in H type ion replacement
separately filled with 10mL of sample and 10mL of cartridge column before being injected into the ion
reaction solution (hexamethyldisiloxane saturated chromatograph.
Fig. 82 Diffusive separation container
47
2.22 Analysis of Microcystin in Blue-green Algae (1) - HPLC
In recent years, social problems are developing as Microcystin is extracted from blue-green algae using acetic
eutrophication takes a stronger grip in lakes such as Lake acid (5%). This is stirred and centrifugally separated in 3
Biwa and Lake Kasumigaura along with the phenomenon repeated operations, then this is cleaned up in accordance
know as blue-green algae. Toxins are manufactured in some with the supernatant. The cleanup operation involves
of the blue-green algae, which form blue-green algae, and passing the supernatant through an ODS cartridge for solid-
there have been examples overseas of cattle dying after phase extraction to adsorb the elements, washing it, then
drinking lake water affected by blue-green algae. solve it out using methanol.
Microcystin is a typical toxin (liver toxin) contained in
blue-green algae, and there are said to be more than 50
kinds of microcystins in the circular peptides made from the
7 amino acids. The representative types found in Japanese
Instrument : LC-VP system
lakes are microcystin LR, YR, and RR.
Column : STR ODS-II (150mm ✕ 6.0mm I.D.)
Mobile phase : 50mM of sodium phosphate buffer
solution (pH 3.0)/methanol = 4/6 (v/v)
References
(1) K.I.Harada, et al.: Toxicon, 26(5), 433-439, 1988
Temperature : 40˚C
(2) K.I.Harada, et al.: J. Chromatogr., 448, 275-283, 1988
Detection : UV-VIS Detector 240nm
Peaks
1. Microcystin RR
2. Microcystin YR
3. Microcystin LR
H CO 2 H R4
N CH2
HN
H 3C O
OCH 3 H O
H H H O
H 3C NH
NH H R3 H
H
H CH 3 CH H R2 HN
3
R1 O
O
H CO 2 H
R1 R2 R3 R4
2 3
Microcystin LR Leu Arg CH 3 CH3
Microcystin YR Tyr Arg CH 3 CH3
Microcystin RR Arg Arg CH 3 CH3
(min)
0 5 10 15
Fig. 83 Microcystin structure Fig. 84 Analysis of blue-green algae
48
Environment Water
2.22 Analysis of Microcystin in Blue-green Algae (2) - HPLC

Reference Example Pretreatment Method Flow Chart
Blue-green algae
Extraction of microcystin
1) 50mL of 5% acetic acid
2) Stir for 30 min
3) Centrifuge
<Repeat operations 1) to 3) three times>
Supernatant
Cleanup with solid-phase extraction method
(Use Sep-Pak Plus tC18)
1) Wash cartridge with 20mL of methanol and 20mL of water
2) Liquid permeation of supernatant in cartridge at 10 to 20mL/min flow speed
(adsorb the microcystin)
3) Wash cartridge with 20mL washing liquid (water/methanol = 9/1)
4) Pour 2mL of methanol into cartridge to solve out microcystin
Solving out (2mL)
HPLC
Sample was provided by Mr. Kunimitsu Hitani of the Environmental Chemistry Division of the National
Institute of Environmental Studies
49
2.23 Analysis of Cyanogen Compounds by Chemical Classification (1) - HPLC
■Explanation
The Ministry of Health and Welfare changed the cyanogens speed liquid chromatography method listed in the drinking
item from a conventional "not to be detected" item to an water testing method is a post column derivative method
item "to be detected" at "0.01mg/L or less" in accordance employing the 4-pyridinecarboxylic acid pyrazolone
with new water quality standards being implemented in method to enable simultaneous analysis of three elements
1993. Also, targeted elements now include cyanogen of cyanogen compounds (cyanogen ion, cyanogen chloride,
chloride in addition to cyanogen ions. For quantifying these and thiocyanic acid).
cyanogens, the conventionally regulated methods have been
Quantitative Range:
the colorimetric method and the ion electrode method using
0.001 or less to 0.2mg/L
the pyridine pyrazolone method and the 4-
Measuring accuracy is within CV 10% at the lower limit
pyridinecarboxylic acid pyrazolone method, but in the
vicinity of quantification
amended drinking water testing method (2001 version),
high-speed liquid chromatography was newly added. This References
measuring method is easier than conventional methods, and Drinking Water Test Method & Explanation (Fiscal 2001
has the merits of being highly sensitive and not easily Volume) 239 - 245
affected by coexisting substances, and more than anything, Japan Water Works Association
the major feature of this method is that it can be used in
analysis of chemical configuration identification. The high-
■Peaks
1 Thiocyanic acid
2 Cyanogen
3 Cyanogen chloride
0 1 2 3 4 5 6 7 (min)
Fig. 85 Chromatogram of cyanogen compound standard samples
50
Environment Water
2.23 Analysis of Cyanogen Compounds by Chemical Classification (2) - HPLC
Instrument : LC-VP system (Detection Conditions) Post column derivative method
[Chlorination]
(Separation Conditions) Reagent solution : 200mM of phosphoric acid (sodium)
Column : Shim-pack AMINO-Na (100mm ✕ 6.0mm buffer solution containing 2mM of
I.D.) chloramine T (pH 6.8)
Mobile phase : 10mM of tartaric acid (sodium) buffer Flow rate : 0.3mL/min
solution (pH 4.2) Reaction unit : SUS coil (2m ✕ 0.3mm I.D.)
Flow rate : 0.6mL/min Temperature : 100˚C
Temperature : 50˚C [Coloring]
Reagent solution : a mixed solution of ethanol solution of
100mM of 1-phenyl 7-3-methyl-5-
pyarozolone and water solution of
20mM of pyridine-4-carboxylic acid
(1/3, V/V)
Reaction unit : SUS coil (2m ✕ 0.5mm I.D.)
Temperature : 100˚C
Cooling unit : SUS coil (2m ✕ 0.3mm I.D.)
Detection : UV-VIS detector 638nm
Apparatus;
1 : Pump for mobile phase
2 : Sample injector
3 : Column oven
4 : Column
5 : Pump for reagent 1
6 : Reaction chamber
7 : Reactor (0.3mm ✕ 2m)
8 : Pump for reagent 2
9 : Reactor (0.5mm ✕ 2m)
10 : Cooling coil (0.3 mm ✕ 2m)
11 : Absorption detector
12 : Data processor
Fig. 86 Analysis system flow route
51
2.24 High-Sensitivity Analysis of Bisphenol A in Environment Water (1) - HPLC
■Explanation
A raw material in polycarbonate resin used in numerous Also, detection of bisphenol A is possible with a UV
industrial products, bisphenol A is suspected as an detector or fluorescence detector, but as complicated
endocrine disruptor compound. Research results indicate coexisting components are more than likely to be found in
that the endocrine disrupting function in bisphenol A is the environment water for analysis, an electrochemical
such that even an extremely trace amount has an affect on detector that can be relied on to be more selective and
organisms. The environment monitoring index is 10ppt highly sensitive was used in this analysis. The following
(ng/L), and there are situations when concentrations lower explains the procedures from induction of sample to
than this index will need to be analyzed. Generally, a transfer to column. (See Fig. 87.)
concentration method (liquid – liquid extraction) is used for
measuring of such low concentrations, which involves a 1) The sample-induction pump and analysis flow channel
cumbersome pretreatment procedure. In the meantime, were connected using a 6-port valve, and sample directly
solid-phase extraction employing a solid-phase extraction fed to pretreatment column.
cartridge could be considered, but this involves automation 2) After constant volume induction of the sample, the valve
difficulties up to the point of analysis. This data introduces was switched, and concentrated bisphenol A was fed
a simple, automatic concentrating analysis method for with mobile phase to the analysis column and analyzed.
bisphenol A using an automatic pretreatment system 3) After elution of bisphenol A at the pretreatment column,
equipped with a polymer type reversed phase column (as a the valve is returned to the original position to prevent
column for pretreatment concentrating). Bisphenol A is entry of coexisting components with tenacious retention
often analyzed using the GC/MS method, but as the power into the column.
derivation reaction needed in this analysis requires a lot of 4) By making one of the ports in the flowchart a washing
time, the more simplified HPLC method can be used; port (using methanol, etc.), the pretreatment column can
however, the above problem also exists in pretreatment. be washed during analysis.
HO OH
6
2
4 7
1
3 5
8
Fig. 87 Flowchart
1: Mobile phase, 2 & 3: Pumps, 4: High-pressure flow channel switching valve, 5: Pretreatment column,
6: Analysis column, 7: Electro chemical detector, 8: Sample (one was distilled water for purge)
52
Environment Water
2.24 High-Sensitivity Analysis of Bisphenol A in Environment Water (2) - HPLC
■Analytical Conditions ■Pretreatment

Instrument : LC-VP system Filtering of 200mL of environment water through a
membrane filter (0.45µm) to create sample.
(Separation Conditions)
Analysis column : Shim-pack VP-ODS(150mm ✕ 4.6mm I.D.) Concentrating column : Shim-pack SPC-RP3
Mobile phase : 20mM sodium phosphate buffer (30mm ✕ 4mm I.D.)
(pH 7) containing 0.1mM EDTA2Na / Sample injection volume : 50mL (pump injection)
acetonitrile = 6/4 (v/v) Sample injection rate : 2.5mL/min
Flow rate : 0.8mL/min Temperature : 40˚C
Temperature : 40˚C
Detection : ESA Coulochem II guard cell 0.6V
1ch 0.35V
2ch 0.55V
0.4
0.4
0.3 0.3
BPA 45.53ppt
mV
0.2
mV
0.2
0.1
0.1 BPA 11.29ppt
0.0
0.0
0 5 10 15 min 0 5 10 15 min
Fig. 88 Analysis example of river water Fig. 89 Analysis example of pond water
53
2.25 Analysis of Alkyl Mercury Compound (1) - GC

There are two methods for measuring mercury in the Instrument : GC-14BPFE
environment – one is the total mercury measuring method Column : Thermon-HG 10% Chromosorb
employing ultraviolet absorption and atomic absorption and W (AW-DMCS)
the other is the organic mercury measuring method 80-100 mesh 0.5m ✕ 3.0mm I.D.
employing gas chromatography (GC). The GC orientated Column temperature : 150˚C
measuring method is known as the effective analysis Injection inlet temperature : 250˚C
method for organic mercury, which was the cause of Detector temperature : 280˚C (ECD)
Minamata disease. As most organic mercury exists in the Carrier gas : N2 40mL/min
environment as methyl mercury and ethyl mercury, GC
enables highly sensitive and selective detection with ECD
using chlorination.
References
Environment Water Quality Analysis Method Manual 411 –
416
Environment Chemical Research Association volume
Quantitative Lower Limit Value (according to
above reference material)
0.5µg/L (for analysis of 200mL sample)
4,983
2,867
Ethyl chloride mercury

Methyl chloride mercury
2✕10–10g
Methyl chloride mercury
Fig. 90 Standard products (100ppb each) Fig. 91 Methyl mercury in snakehead mullet conserved in river A
54
Environment Water
2.25 Analysis of Alkyl Mercury Compound (2) - GC
Reference Example Pretreatment Method Flowchart
200mL sample (500mL separatory funnel used)

When not neutral, ammonia water or hydrochloric acid are used to neutralize before
adding
hydrochloric acid to provide approximately 2N.
Extraction
Add 50mL of benzene, shake well for 2 min, transfer water chamber to separatory
funnel, and store benzene layer. Once again add 50mL of benzene to the water
chamber, stir well for 2 min, and throw away water layer.
Washing the Benzene Layer

Combine benzene layers, add 20mL of sodium chloride solution (200g/L), stir for
approximately 1 min to wash benzene layer, and throw away water layer.
Stripping
Add 8mL of (1) L-cystine and sodium acetate solution to the benzene layer, stir well for
approximately 2 min, allow to stand, then transfer water layer to separatory funnel (20-
30 mL).
Extraction
Add 2mL of hydrochloric acid and 5mL of benzene, shake well for 2 min, allow to
stand, then transfer benzene layer to test tube with joint valve.
GC Analysis
(1) L-cystine and sodium acetate solution

Dissolve hydrochloric acid L-cystine hydrate 1g, sodium acetate trihydrate 0.8g,
and sodium sulphate (anhydrous) 12.8g into water to make 100mL solution.
55
2.26 Analysis of PCB in Water (1) - GC

The polychlorinated biphenyl (PCB) analysis method using Instrument : GC-14BPFE
gas chromatography (GC) is performed using the method Column : OV-1 2% Chromosorb W (AW-
announced by the PCB analytical research group of the DMCS)
Environmental Health Bureau of the Ministry of Health and 80-100 mesh 2.1m ✕ 3.2mm I.D.
Welfare. This method is configured from (1) extraction, (2) : 210˚C
cleanup, (3) separation from agricultural chemicals, (4) Column temperature : 240˚C
confirmation of PCB, and (5) quantifying of total PCB by Injector inlet temperature : 280˚C (ECD)
means of GC with ECD. Detector temperature : N2 40mL/min
Carrier gas
References
Environmental Water Quality Analysis Method Manual 417
– 428
Quantitative Lower Limit Value (according to above

reference material) 1µg/L
ANAL 8
12
16
20
24
28
32
36
4
(min)
Fig. 92 Standard products (KC-300/400/500/600 = 1/1/1/1) 1ppm chromatogram
56
Environment Water
2.26 Analysis of PCB in Water (2) - GC
Reference Example Pretreatment Flowchart
Sample 1L (2L separatory funnel used)
50mL of acetone
50mL of n-hexane
Extraction
2nd measure of 50mL of n-hexane (throw away water layer)
Concentration (K-D concentrator used) 5mL
Silica gel column chromate tube elution test

1. Activation 30min cooling at 130°C 18 hr by desiccator
2. Mixture (2:1) of KC-300, KC-600, 10ppm n-hexane
3. Chromate tube 10mm *30cm
Washing with absorbent cotton or glass wool
permeated with 10mL of n-hexane
Filling Place 4g of silica gel and 10mL of n-hexane in beaker.
Flow down n-hexane... stabilize silica gel layer.
Place 1g of Sodium sulphate (anhydrous) on top of silica gel.
2mL of separate screen test solution
(dropping as far as the sodium sulphate surface)
Wash inside of chromate tube twice (1mL each time)
Attach 300mL separatory funnel, divide 200ml of n-hexane
effluent into 10mL batches in 20 test tubes.
GC Analysis 5 µm injection
(Confirm stability and collection rate of run-off range 2 or 3 times.)
Reference example)
1. Silica gel column (Wakogel S-1)
10mm internal diameter of glass, silica weight 4g, height 220mm
Runoff n-hexane with valve fully open, runoff speed 2.6mL/min.
2. Florisil PR
10mm internal diameter of glass, florisil weight 4g, height 120mm
Runoff n-hexane with valve fully open, runoff speed 10.5mL/min.
57
2.27 Analysis of Residual Organic Phosphorus Compounds (1) - GC

In order to prevent water pollution in Japanese water Instrument : GC-17AAFwFp
catchments for public use, the organic phosphate Column : DB-1 30m ✕ 0.25mm I.D.,
compounds - parathion, methylparathion, EPN, and 0.25µm(df)
methyldimeton – are regulated in the standard items Column temperature : 50˚C(2min)-10˚C/10min/-270˚C
concerning water discharged from factories into water -270˚C(10min)
catchments for public use. Injection inlet temperature : 250˚C
Detector temperature : 270˚C (FPD P mode)
References
Carrier gas : He 1.5mL/min, H2 95mL/min,
New discharge standards and their analysis methods 161 –
Air 65mL/min
165
Injection method : Splitless
Environment Chemical Research Association Volume
(Water Quality Standards Section edition of the Water
Quality Bureau of the Environment Agency)
Quantifying Lower Limit Value(according to above
reference material) : 0.1mg/L
Methylparathion
Parathion
Methyldimeton
EPN
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
18.0
20.0
22.0
24.0
26.0
28.0
(min)
Fig. 93 Standard products (1ppm each) chromatogram
58
Environment Water
2.27 Analysis of Residual Organic Phosphorus Compounds (2) - GC
Reference Example Pretreatment Method Flowchart
Sample 100mL
5g of sodium chloride
Adjust to pH 3 – 4 with hydrochloric acid (1 + 1)
Extraction
Extract 40mL of n-hexane twice.
Add sodium sulphate (anhydrous) to n-hexane to remove water.
Volatize the n-hexane.
Conversion Solution (10mL of acetone)
GC Analysis 2µL
59
2.28 Analysis of Volatile Organic Compound (VOC) in Wastewater and
Environment Water using Head Space Method (1) - GC/MS
In addition to the amendments to the water quality standard Sample : 10ml+NaCl3g
in tap water in December 1992 and the environment Perkin Elmer HS-40
standard for environment water suitable as a source of Sample temp. : 60˚C
drinking water in March 1993, a further amendment was Condition time : 30min
also implemented for the wastewater standard in February Needle temp. : 120˚C
1994. The analysis of the compounds itemized in these Transfer temp. : 150˚C
amendments is performed using the head space method, the Pressueriz. time : 2min
solvent extraction method, and the purge trap method. Here, Injection time : 0.20min
the head space method has the features of being easy to
operate, has good reproducibility, an auto sampler can be Shimadzu GCMS-QP5050A
used, and carry over (pollution levels of conventional Carrier gas : He120kPa
analytical instruments caused by components with high Column : DB624 60m ✕ 0.32mm I.D.
concentration levels) is minimal. 1.8µm(df)
References Column temp. : 40˚C(2min)-10˚C/min-200˚C(2min)
Drinking Water Test Method & Explanation Japan Water
Works Association volume
Environment Water Quality Analysis Manual
New wastewater standards and their analysis methods
TIC 19 93377
14
20
9
17
1 3 67
2 13 1516
8 1011 18 22
4 5 12 21 IS
6 8 10 12 14 16 18 20 (min)
Fig. 94 Analysis example of standard sample (VOC 2ug/L)
TIC 83186
5
12
9
14
18
6 19 21
2 20
6 8 10 12 14 16 18 20 (min)
60
Environment Water
2.28 Analysis of Volatile Organic Compound (VOC) in Wastewater and

Environment Water using Head Space Method (2) - GC/MS
TIC
14 64907
6 17 19
9
4 5 10 20
2 12
1
22
6 8 10 12 14 16 18 20 (min)
Fig. 96 Analysis example of wastewater
Wastewater,
Environment Water Sewage,
ID Name Tap Water (mg/L) Soil (mg/L)
(mg/L) Industrial waste
(mg/L)
1 1,1-dichloroethene 0.02 Same as left Same as left 0.2
2 Dichloromethane 0.02 Same as left Same as left 0.2
3 trans-1,2-dichloroethane 0.04 Same as left — —
4 cis-1,2-dichloroethane 0.04 Same as left Same as left 0.4
5 Chloroform 0.06 Same as left — —
6 1,1,1-trichloroethane 0.3 1.0 1.0 3.0
7 Tetrachloromethane 0.002 Same as left Same as left 0.02
8 1,2-dichloroethane 0.004 Same as left Same as left 0.04
9 Benzene 0.01 Same as left Same as left 0.1
10 Trichloroethene 0.03 Same as left Same as left 0.3
11 1,2-dichloropropane 0.06 Same as left — —
12 Bromodichloromethane 0.03 Same as left — —
13 cis-1,3-dichloropropene *1 Same as left Same as left *3
14 Toluene 0.6 Same as left — —
15 trans-1,3-dichloropropene *1 Same as left Same as left *3
16 1,1,2-trichloroethene 0.006 Same as left Same as left 0.06
17 Tetrachloroethene 0.01 Same as left Same as left 0.1
18 Dibromochloromethane 0.1 Same as left — —
19 m,p-xylene *2 Same as left — —
20 o-xylene *2 Same as left — —
21 Bromoform 0.09 Same as left — —
22 p-dichlorobenzene 0.3 Same as left — —
IS p-bromofluorobenzene
*1: Total 0.002mg/L
Chart 16 Names of measured target compounds together with standard values and indicator values *2: Total 0.4mg/L
*3: Total 0.02mg/L
—: Not regulated
61
2.29 Analysis of Volatile Organic Compound (VOC) (P/T Method) - GC/MS
■Explanation Desorption time : 3 min

Some 300 components were listed as items requiring Cryo focus : -190˚C
studies as part of the effort to protect water environments temperature
created by the Japanese Ministry of the Environment in Cryo injection : 200˚C
1998. This data introduces measuring results for VOC temperature
compounds in that list. GC
Column : Aquatic (60m ✕ 0.25mm I.D. df
Reference
= 1.0µm)
Column temperature : 40˚C (5 min) -7˚C/min
■Analytical Conditions -220˚C (5 min)
Purge & Trap Injection inlet temperature : 250˚C
Trap tube : GL-Trap1 Carrier gas : He 100kPa
Purge temperature : 35˚C MS
Purge time : 2.5min Ionization : EI
Purge flow rate : 30mL/min Scan range : m/z 29 - 300
Desorption temperature : 200˚C Monitored mass : See Chart 17
ID Compound SIM ID Compound SIM
1 Chloromethane 50.00 52.00 11 1,1-Dichloroethane 83.00 63.00

2 Vinyl chloride 64.00 62.00 12 1-Bromopropane 122.00 124.00
3 1,3-Butadiene 54.00 39.00 13 Bromochloromethane 130.00 128.00
4 Bromomethane 94.00 96.00 14 Bromodichloromethane 83.00 85.00
5 Chloroethane 64.00 66.00 15 Dibromochloromethane 129.00 127.00
6 Allyl chloride 78.00 76.00 16 Chlorobenzene 112.00 77.00
7 Cycropentane 55.00 70.00 17 1,1,1,2-Tetrachloroethane 131.00 117.00
8 Methyl-t-butylether 57.00 73.00 18 Ethylbenzene 106.00 91.00
9 n-Hexane 86.00 57.00 19 1,1,2,2-Tetrachloroethane 83.00 85.00
10 2-Bromopropane 122.00 124.00 20 1,2,3-Trichloropropane 110.00 75.00
Chart 17 Monitor mass list
79
TIC 3000000
16
17
6 18
10
4
3 11 12
13
8 19
20
5
2
14
1
15
5 10 15 20 25 30
Fig. 97 Total ion chromatogram
62
Environment Water
2.30 Analysis of Estradiol - GC/MS

17β-Estradiol is monitored using GC/MS because it is a Column : DB-5H (30m ✕ 0.25mm I.D. df
chemical substance suspected of having an endocrine = 1.0µm)
disrupting effect. Electron ionization is used as the Column temperature : 50˚C (2min) -20˚C/min -250˚C
ionization mode for MS, but this data introduces -5˚C/min -300˚C (5min)
measurements taken using negative chemical ionization Injection inlet temperature : 280˚C
(NCI). Carrier gas : He 120kPa
Injection method : Splitless (2.0min/250kPa)
Reference
MS
Ionization : NCI (Isobutane)
Scan range : m/z 29 - 700
Monitored mass : 343, 269, 367, 431, 347
Water Sample Sediment & Organism Sample

1L water sample Surrogate addition 10g sample Surrogate additive
pH 5 acetate buffer Methanol & pH acetate buffer (9:1)
Solid-phase extraction C18 cartridge Extraction
Cleaning using 5mL purified water & 5mL hexane

Methanol/hexane distribution
Eluation 5mL methanol
Fragment methanol and add water
Dichloromethane extraction Solid-phase extraction of sediment
Desiccation N2 purge
Florisil/C18 cartridge
Purifying prior to derivatization
PFB derivatization 0.5mL PFB reaction liquid GPC column, etc.
6mL water, 2mL hexane Desiccation N2 purge

Hexane layer dehydrating, exsiccation Anhydrous Na2SO4 & N2 purge
PFB derivatization 0.5mL PBB reaction liquid
TMS derivatization TMS imidazole 6mL water, 2mL hexane
Hexane layer dehydrating, desiccation Anhydrous Na2SO4 & N2 purge
Silica gel mini column
Hexane washing Florisil column
Hexane washing
Hexane: Ethyl acetate (9:1) elution
GC/NCI-MS
TMS derivatization TMS imidazole
Silica gel mini column

Fig. 98 Pretreatment flow Hexane washing
GC/NCI-MS
OH OH
PFB derivatization F 65000000

F 60000000 -estradiol + d
HO O 55000000 Estoron
50000000
F F a-estradiol
TIC
45000000 Ethynyl estradiol
17 -Estradiol F Si 40000000 Estriol
*1.00
O 35000000
343.20
*1.54
30000000 269.10
25000000 *1.50
TMS derivatization F 20000000
347.30
*1.76
F 15000000 367.20
O 10000000 *1.63
5000000 431.30
F F *1.77
0
F 13 14 15 16 17 18 19 20 min
Fig. 99 Derivatization Fig. 100 Total ion chromatograms of estradiol types
63
3. Wastewater
3.1 Analysis of Anions in Wastewater - Ion Chromatograph
Fluoride, nitrate nitrogen and nitrite nitrogen are raised as Filtering through a membrane filter (0.45 µ m) for ion
necessary monitoring items in the water environment chromatography
standards, and the ion chromatography method is one of the
monitoring methods employed. Non-organic ions in ■Analytical Conditions
wastewater are one of the causes of pollution and Instrument : Ion chromatograph
eutrophication in rivers and lakes, and pollution is Column : Shim-pack IC-A1 (100mm ✕ 4.6mm I.D.)
approaching a critical stage due to abnormal drought in Mobile phase : 2.5mM of phthalic acid, 2.4mM Tris
recent years and neglect in the area of sewage facility (hydroxymethyl) aminomethane
provision. Thus, the importance of monitoring non-organic Flow rate : 1.5mL/min
ions in wastewater has increased. Temperature : 40˚C
Detector : Electric conductivity detector
References
(1) Drinking Water Test Method & Explanation (Fiscal
1993 Volume) 164 – 198
Ministry of Health and Welfare, Environ. Health
Bureau, Water Supply & Environ, Sanitation Dept.
edition
(2) New wastewater standards and their analysis methods
400 – 406
Water Quality Standards Section edition of the Water
Quality Bureau of the Environment Agency
Environment Chemical Research Association
■Peaks
–
1 PO43
–
2 Cl
–
3 NO3
2–
4 SO4
Fig. 101 Analysis of wastewater
64
Wastewater
3.2 Analysis of Cations in Wastewater - Ion Chromatograph
■Pretreatment
Filtering through a membrane filter (0.45 µ m) for ion
chromatography
Instrument : Ion chromatograph
Column : Shim-pack IC-C1 (100mm ✕ 4.6mm I.D.)
Mobile phase : 5mM of nitric acid
Temperature : 40˚C
Detector : Electric conductivity detector
■Peaks
+
1 Na
+
2 NH4
+
3K
Fig. 102 Analysis of wastewater
65
3.3 Analysis of Anions in Wastewater - PIA-1000

This is an analysis example where the personal ion analyzer Instrument : PIA-1000
PIA-1000 was used to analyze anions contained in Column : Shim-pack IC-A3(S)
processed water at a sewage works. Mobile phase : PIA-1000 dedicated anion analysis mobile
phase, IC-MA3-1
■Pretreatment Temperature : 35˚C
Filtering through a membrane filter (0.45 µ m) for ion
chromatography
■Peaks
–
1 HCO3 (31.01mg/L)
3–
2 PO4 (3.245mg/L)
–
3 F (0.169mg/L)
–
4 Cl (60.59mg/L)
–
5 NO3 (47.47mg/L)
2–
6 SO4 (56.54mg/L)
Fig. 103 Analysis of wastewater (PIA-1000)
66
Wastewater
3.4 Analysis of Cations in Wastewater - PIA-1000

This is an analysis example where the personal ion analyzer Instrument : PIA-1000
PIA-1000 was used to analyze cations contained in Column : Shim-pack IC-C3(S)
processed water at a sewage works. Mobile phase : PIA-1000 dedicated cation analysis
mobile phase, IC-MC3-1
■Pretreatment Flow rate : 0.2mL/min
Filtering through a membrane filter (0.45 µ m) for ion Temperature : 35˚C
chromatography
■Peaks
+
1 Na (58.20mg/L)
+
2 NH4 (0.558mg/L)
+
3 K (10.55mg/L)
+
4 Mg2 (5.814mg/L)
2+
5 Ca (29.29mg/L)
Fig. 104 Analysis of wastewater (PIA-1000)
67
3.5 Analysis of Volatile Organic Compound (VOC) in Wastewater - GC

In 1993, the environment standard for environment water Instrument : HSS-4A + GC-17AAE
was greatly amended, and the wastewater standard items Column : DB-VRX 75m ✕ 0.45mm
became 24 items. And among these, VOC occupies 11 I.D., 2.55µm(df)
items. Environment water analysis is mostly conducted Column temperature : 35˚C(5min)-180˚C(5˚C/min)
using GC/MS, but GC can be used for analyzing just those Injection inlet temperature : 200˚C
samples that have small amounts of impurities in them. Detector : ECD 210˚C
This data is an example of analysis for water with VOC Carrier gas : He 6.0mL/min
component using head space GC. This method can be used Head space heat-reserving conditions : 50˚C, 60min
to analyze 10 of the items in the items of the wastewater Head space injection volume : 0.2mL (inject total volume)
standard.Benzene needs to be analyzed using FID as it
cannot be detected by ECD.
Quantifying Lower Limit Value (target): This greatly
differs depending on the element.
★
1,1 Dichloroethylene
★ ★
Carbon tetrachloride
p-Dichlorobenzene
Dichloromethane
Trans-1, 2 Dichloroethylene
★
★
Tetrachloroethylene
Cis-1, 2 Dichloroethylene
★
Bromodichloromethane
30. 0
32. 0
★
1, 1, 1-trichloroethane
8. 0
10. 0
12. 0
14. 0
Dibromochloromethane
★
Trichloroethylene*
★
★
Trana-1, 3 -dichloropropene
Cis-1, 3 -dichloropropene
★
1, 1, 2-trichloroethane
★
1,1-dichloroethylene
1, 2-dichloroethane
Chloroform
Bromoform
Dichloromethane
1,2-dichlorobro
0. 0
2. 0
4. 0
6. 0
8. 0
10 . 0
12 . 0
14 . 0
16 . 0
18 . 0
20 . 0
22 . 0
24 . 0
26 . 0
28 . 0
30 . 0
32 . 0
Fig. 105 Analysis example of VOC in environment water using head space GC-ECD (* signifies regulated item of wastewater standard)
68
4. Atmosphere
4.1 Analysis of Acidic Substances in Exhaust Gas - Ion Chromatograph
Analysis of acidic gas existing in exhaust gas was Filtering through a membrane filter (0.45 µ m) for ion
performed. The analysis targets, HC1, NOx, and SOx, were chromatography
individually absorbed into absorption solutions, then
analyzed by an ion chromatograph. Figure 109 shows the ■Analytical Conditions
results for analysis of a solution obtained by absorbing HC1 Instrument : Ion chromatograph
from exhaust gas into 0.4% NaOH. Figure 107 shows the Column : Shim-pack IC-A3 (150mm ✕ 4.6mm
results for analysis of NO3– created by absorbing NOx from I.D.)
exhaust gas into a mixed solution H2O2– and Sulfuric acid. Guard column : Shim-pack IC-GA3 (10mm ✕ 4.6mm
Figure 108 shows the results for analysis of SO42– created by I.D.)
absorbing SOx from exhaust gas into H 2O 2. All three Mobile phase : 5.0mM p-hydroxybenzoic acid, 3.0mM
samples can be measured at high sensitivity without any Bis-Tris*
special pretreatment. Flow rate : 1.5mL/min
Temperature : 40˚C
*Bis-Tris : Bis (2-hydroxyethyl) iminotris
■Peaks ■Peaks ■Peaks

– – –
1 Cl (95.6ppm) 1 Cl (0.42ppm) 1 Cl (49.0ppm)
– – –
2 SO42 (66.1ppm) 2 NO3 (1.98ppm) 2 SO42 (7.94ppm)
2–
3 SO4 (9.14ppm)
Fig. 106 Analysis of HC1 in exhaust gas Fig. 107 Analysis of NOx in exhaust gas Fig. 108 Analysis of SOx in exhaust gas
69
4.2 Analysis of Exhaust Gas Absorption Solution - PIA-1000
Analysis examples using the personal ion analyzer PIA- Filtering through a membrane filter (0.45 µ m) for ion
1000 are shown in figure 109 with absorption solution for chromatography
exhaust gas of supply water boiler (vacuum flask method)
and figure 110 with absorption solution for exhaust gas of a ■Analytical Conditions
garbage and sewage plant (vacuum flask method). The PIA- Instrument : PIA-1000
1000 enables highly sensitive analysis. Column : Shim-pack IC-A3(S)
Mobile phase : PIA-1000 designated ion analysis mobile
Flow rate phase, IC-MA3-1
Temperature : 0.2mL/min
: 35˚C
■Peaks
–
1 Cl (0.263mg/L)
–
2 NO3 (1.969mg/L)
2–
3 SO4 (4.172mg/L)
Fig. 109 Analysis of supply water boiler exhaust gas absorption solution
■Peaks
–
1 Cl (6.332mg/L)
–
2 NO3 (2.394mg/L)
2–
3 SO4 (1.029mg/L)
Fig. 110 Analysis of garbage and sewage plant exhaust gas absorption solution
70
Atmosphere
4.3 Analysis of Tolylenediisocyanate (TDI) in Work Environment Monitoring (1) - HPLC
In 1995, partial amendments were made to the work After collecting a sample for 10 min in 1-(2-pyridyl)
environment evaluation standard and the work environment piperazine impregnated filter paper at a gas suction flow
monitoring standard. High-speed liquid chromatography rate of 1L/min, remove sampling filter paper, and extract
was added to the analysis methods currently being used for sample using a shaker with 4mL of methanol containing
ethyleneimine, 3, 3'-dichloro-4, 4'-diaminodithanylmethane, acetic acid. Filter the extracted solution through a 0.45µm
and tolylenediisocyanate (TDI). Among these TDI is membrane filter to make a test solution.
greatly used in materials such as the raw material of
polyurethane foam, polymerization of cross linked agents, ■Analytical Conditions
foaming agent, paints, and glues, and is strongly toxic to the Device : LC-VP system
human body, which, in cases of acute poisoning, can cause Column : STR ODS-II (150mm ✕ 4.6mm I.D.)
pneumonia and tuberculosis, that can lead to fatalities due Mobile phase : 50mM of sodium acetate buffer solution
to weakening of the heart if the illness becomes serious. (pH 6.2)/acetonitrile = 68/32 (v/v)
Currently, the value for the work environment standard has Flow speed : 1.5mL/min
been amended to 5 ppb, and a measurement level of one Temperature : 40˚C
tenth of this, 0.5 ppb, is requested. Here, a suitable testing Detector : UV-VIS detector 247nm
method is the high-speed liquid chromatograph method,
which is highly sensitive in comparison to conventional
diazotization coupling absorptiometry, and has many
features such as the capability of being able to separately
quantify isomers.
Reference
Kenji Nakaaki, Shinya Koike, Yuriko Takada: Labor
Science, 63 (1), 1-13, 1987
0.5
Reagent decomposition matter
mAbs
2,6-TDI
2,4-TDI
0 2 4 6 8 (min)
Fig. 111 Analysis of TDI gas sample (0.5 ppb suitable for each)
71
4.3 Analysis of Tolylenediisocyanate (TDI) in Work Environment Monitoring (2) - HPLC
Reference Example 1 Sampling and Pretreatment Method
Sample 10L
Sampling
Collect sample for 10 min in 1-(2-pyridyl) piperazine
impregnated filter paper at a gas suction flow rate
of 1L/min.
Extraction
Add 4mL of methanol (containing acetic acid of 0.05v/v%)
and shake for 30 min.
Filtration
Use a 0.45 µm membrane filter.
HPLC 20 µL Injection
Reference Example 2 Flow Diagram for TDI Generation Device
Nitrogen cylinder Humidification device
Nitrogen cylinder Standard gas generator
Trap
Glass board for sampling
Solid-phase collecting
Humidity sensor
Exhaust
Sample provided by Japan Work Environment Monitoring Association.
72
Atmosphere
4.4 Analysis of Aldehyde/Ketonic products in Exhaust Gas - HPLC

This shows an example of analysis performed on Device : LC-VP system
aldehyde/ketonic products found in vehicle exhaust gas. Column : STR ODS-II (150mm ✕ 6.0mm I.D.)
In cases where exhaust gas is set as the sample, and Mobile phase : A / B gradient elution method
negative-phase chromatography is used to separate and A: Water/THF/methanol = 70/10/20
detect absorbance, the type of impurities and the amount (v/v/v)
of content often lead to difficulties in analysis. In B: Water/acetonitrile, = 30/70 (v/v)
particular, impurity peaks are sometimes observed as Flow rate : 1.0mL/min
peak overlay and warping for formaldehyde peaks that Temperature : 45˚C
solve out quickly. In such cases, these affects can be Detector : UV-VIS detector 365nm
avoided by adding methanol to mobile phase A solution.
■Pretreatment
Conforming to JIS Law (K0303)
Sample kindly lent by Traffic Safety and Nuisance
Research Institute of the Ministry of Transport.
1 Peaks:
1. Formaldehyde
2. Acetone
3. 2-Butanone
2
3
0.0 3.0 6.0 9.0 12.0 15.0 18.0 21.0 24.0 27.0
(min)
Fig. 112 Analysis of aldehyde/ketonic products in exhaust gas
73
4.5 Analysis of Aldehyde/Ketonic products in Room Atmosphere (1) - HPLC

With regard to the monitoring regulations and analysis Device : LC-VP system
methods for harmful pollutants in the air, the American Column : STR ODS-II (150mm ✕ 6.0mm I.D.)
Environmental Protection Agency (EPA) has already listed Mobile phase : A / B gradient solving out method
recommended analysis methods for 189 compounds with A: Water/THF/methanol = 70/10/20
the Clean Air Act. Here, an example of analysis of general (v/v/v)
residential room air in accordance with the aldehyde B: Water/acetonitrite = 30/70 (v/v)
analysis method recommended by the EPA is introduced. Flow rate : 1.0mL/min
Temperature : 45˚C
■Pretreatment Detector : UV-VIS detector 365nm
Sample air was made to pass through silica gel cartridge
coated with dinitrophenylhydrazine (DNPH) in acidified
state, after trapping each aldehyde/ketonic product as
DNHP derivatives, they were extracted by solving out with an
organic solvent. This enables high-scale concentration. In
the case of this sample, the DNPH cartridge was attached
directly to an on-site sampling pump (SHIMADZU VPC-
10), the sample concentrated, and solved out with
acetonitrite to make the test solution.
Peaks:
1 1. Formaldehyde
2. Acetaldehyde
3. Acrolein
4. Propionaldehyde
5. Methacrolein
6. n-Butyraldehyde
7. Benzaldehyde
8. Valeraldehyde
9. Hexanaldehyde
2
3
5
9
4 6 7 8
0.0 4.0 8.0 12.0 16.0 20.0 24.0 28.0 32.0

(min)
Fig. 113 Analysis of aldehyde/ketonic products in a child's room
74
Atmosphere
4.5 Analysis of Aldehyde/Ketone in Atmosphere (2) - HPLC
Instrument : LC-2010
Column : Shim-pack FC-ODS (75mm ✕ 4.6mm I.D.)
Mobile phase : A / B gradient elution method
: A: Water/THF = 8/2, (V/V)
: B: Acetonitrile
Temperature : 40˚C
Detection : UV-VIS detector 365nm
Chromatograms
2nd analysis of room air

(Acetone in use)
1st analysis of room air
Cartridge blank
Fig. 114 Measuring example of formaldehyde in room air
75
4.6 Analysis of Aldehyde Types in Atmosphere (1) - GC
There are 13 kinds of harmful air pollutants (substances that Air-borne aldehyde is changed to a derivative (aldehyde
can be harmful to human health if in imbibed on a regular DNPH) using 2, 4-dinitrophenylhydrazine when
basis and cause actual air pollution), and this section concentrated and collected, and is measured against a
introduces the air-borne aldehyde type. Under the Offensive nitrogen compound using a highly sensitive and selective
Odor Control Law, factories are obligated to monitor FTD (thermal ionization detector).
aldehydes at their site perimeters.
References Device : GC-17AAFwFt
Actual Monitoring of Harmful Air Pollutants 157 – 200 Column : DB-1 30m ✕ 0.25mm I.D.,
(1997) Environment Agency, Air Quality Bureau, Air 0.25µm(df)
Regulation Section Edition Column temperature : 80˚C(2min)-20˚C/min-90˚C
Quantitative Lower Limit Value (target quantitative -3˚C/min-230˚C
lower limit value according to above reference Injector inlet temperature : 250˚C
material) Detector temperature : 280˚C(w-FTD)
Formaldehyde 0.8µg/µm3 (provisional value) Carrier gas : He 2.9mL/min
Acetaldehyde 0.5µg/m3 Injection method : Splitless (1min)
This is an example of analysis of formaldehyde,

acetaldehyde together with elements
DPA(IS)
(propionaldehyde, butylaldehyde, and

valeraldehyde) targeted by the Offensive Odor
Control Law, as well as ketonic substances that
reacts with DNPH. Diphenylamine (DPA) was
used as the internal standard substance
Form
(Fig. 115).
Propion
Acetone
Acet
i-Butyl
n-Butyl
n-Valer
i-Valer
MEK
MIBK
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 (min)
Fig. 115 Analysis example of aldehyde DNPH types

This shows an example of actual air collected
DPA(IS)
and analyzed (Fig. 116).

Acetone
Form
Propion
n-Butyl
n-Valer
MEK
i-Butyl
Acet
MIBK
i-Valer
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 (min)
Fig. 116 Analysis example of aldehyde types in the environment
76
Atmosphere
4.6 Analysis of Aldehyde Types in Atmosphere (2) - GC
Reference Example Pretreatment Method
■Sample Collection Method ■Cartridge Solving Out Method

Two marketed cartridges impregnated with 2, 4- Aldehydes react in the cartridges to form aldehyde-DNPHs,
dinitrohydrazine are used in tandem. Pump flow rate is set and are solved out using acetonitrile. DNPH is also solved
to be about 0.1 L per minute, and collection is performed out at this time using a positive ion replacement resin as it
continuously for 24 hours. The used air volume is measured can interfere with analysis. As the solving out solvent
with a flowmeter. To prevent the breakup of aldehyde acetonitrile is sensitive to FTD, it is solved into ethyl
DNPH by air-borne ozone, an ozone scrubber cartridge is acetate to make a sample solution (Fig. 118).
attached to the front of the collection cartridge system (Fig.
117).
Fig. 117 Sample collection method Fig. 118 Solving out method from cartridge
77
4.7 Analysis of Formaldehyde in Room Atmosphere - UV
■Explanation ■Monitoring Device

Formaldehyde residue sometimes exists in wall materials Concentrated collection device : VPC-10
and flooring of homes, and this residue is dispersed as a Spectrophotometer : UV-1600 standard
vapor in house air. Consequently, monitoring the glass cell
concentration of such formaldehyde has become an
important task. Here, experimental monitoring was
performed in the rooms of a new house using a combination
of a solution collection method with water and an
acetylacetone colorimetric method.
Reference Material
JIS K0303 Monitoring of HCHO in exhaust gas
Quantitative lower Limit (target): several 10ppb
Standard sample
Put 40mL volumes of absorption solution (distilled water) into absorption beakers 1 & 2. 1.100
A 1.000
/
b
s
Sampling (flow rate 1 L/min, collection time 20 or 40min) o
r
/
b 0.500
Retrieve absorption solution, and measure up to 100mL with distilled water. a
n
//
c
e
5mL of purifying water for 5mL of test solution 0.000
1.000 2.000 3.000 4.500
creation of calibration curve for concentration measuring ˜/P
Wavelength : 412.0
//
//
5mL of formaldehyde STD 5mL of test solution

/
Slit amplitude: 2.0

/
Add 5mL of acetylacetone reagent add 5mL of purified water

Multi-point calibration curve
/
/
/
Conc=K1 A+K0
Heat for 30min in heating solution (40+2;)
– K1=3.762 k0=0.00526
/
/
/
Keep at room temperature for 30min Chi-Square : -0.00118

Reagent BL STD Measured sample Sample BL Data points : 6
ID Concentration Absorbance
Fig. 119 Measuring flowchart for formaldehyde in air 1 0.08126 0.020
1 0.08051 0.020
Average : 0.08088 0.020 /Room 1 results (in absorption solution)
Standard deflection :
2 0.1452 0.037
2 0.1459 0.037
3 0.06170 0.015
3 0.05793 0.014
Measurement results for formaldehyde in air
Room 1: 0.302ppm(20min)
Fig. 120 Measuring example of formaldehyde in air
78
Atmosphere
4.8 Analysis of Volatile Organic Components (VOC) in Atmosphere(1)

- Solid-phase Adsorption & Thermal Desorption GC/MS
■Explanation –– Tube ––
Various substances that are harmful to human health are This is comprised of a glass or stainless tube filled with
being found in ambient air, and though the concentrations adsorption material. The adsorption material is graphite
may not be enough to harm human health directly, there are carbon black, carbon molecular sieves. These are used in
fears that exposure over time can lead to cancer, etc. With multiple bed form to match targeted sample.
this as a background consideration, a law partially
References
amending the Air Pollution Control Law was introduced in
(1) Actual Measuring of Harmful Air Pollutants
May 1996, and put into practice from April 1st, 1997. The
Publisher: Editing Committee for Actual Measuring of
Central Council for Environmental Pollution Control
Harmful Air Pollutants
published via the second verdict in October 1996 a list of
(2) Manual of Measuring of Harmful Air Pollutants
234 substances that are potentially harmful air pollutants
Environment Agency, Air Quality Bureau, Air
(HAPs), among which 22 types are listed as being
Regulation Section Edition
substances that require priority action. In February 1997, an
environment standard for annual average of benzene
0.003mg/m3, trichloroethene 0.2mg/m3, tetrachloroethene
0.2mg/m 3 was announced to cover air pollution. The
analysis method for monitoring this standard involves solid-
phase adsorption and thermal desorption. The analysis in
this method involves sampling VOC in the atmosphere for
24 hours using a tube.
Ambient air Dehydration

tube Adsorption tube
Flowmeter Suction
pump
Fig. 121 Sampling with tube collection method
Fig. 122 Continuous air sampler
79
4.8 Analysis of Volatile Organic Components (VOC) in Atmosphere (2)
- Solid-phase Adsorption & Thermal Desorption GC/MS
Thermal desorption ATD-400
Collection tube separation : 280˚C(5miin)
Separation flow speed : 50mL/min
Second trap separation : 280˚C(2min)
Outlet split : 8mL/min
Shimadzu GCMS-QP5050A
Column : DB-1 60m ✕ 0.32mm I.D.,
5µm(df)
Column temperature : 40˚C(5min)-5˚C/min-150˚C
-10˚C/min-250˚C(5min)
Carrier gas : He 100kPa Fig. 123 ATD-400 system principle
TIC 7 127756
ID Name
5
1 Chloroethene
2 1,3-butadiene
2
3 Acrylonitrile
4 Dichloromethane
1 8
3 5 Chloroform
6
4 9
6 1,2-dichloroethane
7 Benzene
8 Trichloroethene
9 Tetrachloroethene
6 8 10 12 14 16 18 20 22 24 26 (min)
Fig. 124 Analysis example (SIM method) of Nine HAPs elements (1ppm ✕ 10mL)
MIC 2000000
n-Hexane
Dichloromethane
Chloroform
Ethanol
Toluene
Ethyl benzene
Styrene
m, p-Xylene
Freon 12
Benzene
5 10 15 20 25 30 35 (min)
Fig. 125 Measuring example (SCAN method) of lab air
80
Atmosphere

- Container Collection Method GC/MS
■Explanation
Various substances that are harmful to human health are of a collection canister (inert processed metal airtight
being found in ambient air, and though the concentration sealing) used to sample the VOC in the atmosphere for 24
may not be enough to harm human health directly, there are hours.
fears that exposure over time can lead to cancer, etc. With
–– Canister ––
this as a background consideration, a law partially revising
The canister is an airtight, spherical container, which is
the Air Pollution Control Law was introduced in May 1996,
specially processed to be inert by being formed from a
and put into implementation from April 1st, 1997. The
metal construction with electro polished inner surface and
Central Council for Environmental Pollution Control
pure chrome-nickel oxide thin film (SUMMA®).
published via the second verdict in October 1996 a list of
234 substances that are potentially harmful air pollutants References
(HAPs), among which 22 types are listed as being (1) Actual Measuring of Harmful Air Pollutants
substances that require priority action. In February 1997, an Publisher: Editing Committee for Actual Measuring of
environment standard for annual average of benzene Harmful Air Pollutants
0.003mg/m3, trichloroethene 0.2mg/m3, tetrachloroethene (2) Manual of Measuring of Harmful Air Pollutants
0.2mg/m 3 was announced to cover air pollution. The Environment Agency, Air Quality Bureau, Air Pollution
analysis method called container collection involves the use Control Edition
MIC 30 84230717
2
20
3 9 26
29
4 19 31 34 40
11 28
5 10 32 35 37
15 25 36
1 21
7 13 14 23 33 38
12 16 18
8 39
6
17 22
27
24
IS
5 10 15 20 25 30 (min)
1 Freon12 15 Chloroform 29 Ethylbenzene

2 Freon114 16 1,1,1-trichloroethane 30 m,p-xylene
3 Chloromethane 17 Carbon tetrachloride 31 o-xylene
4 Chloroethene 18 1,2-dichloroethane 32 Styrene
5 1,3-butadiene 19 Benzene 33 1,1,2,2-tetrachloroethane
6 Bromomethane 20 Trichloroethene 34 1,3,5-trimethylbenzene
7 Chloroethane 21 1,2-dichloropropane 35 1,2,4-trimethylbenzene
8 Freon11 22 cis-1,3-dichloropropene 36 m-dichlorobenzene
9 Freon113 23 Toluene 37 p-dichlorobenzene
10 1,1-dichloroethene 24 Trans-1,3-dichloropropene 38 o-dichlorobenzene
11 Acrylonitrile 25 1,1,2-trichloroethane 39 1,2,4-trichlorobenzene
12 Dichloromethane 26 Tetrachloroethene 40 Hexachloro-1,3-butadiene
13 1,1-dichloroethane 27 1,2-dibromoethane IS Toluene-d8
14 cis-1,2-dichloroethene 28 Chlorobenzene
Fig. 126 EPA TO14+2 elements (1, 3-butadiene, acrylonitrile) 10ppbv
81
- Container Collection Method GC/MS
Reference Example 1
Control valve
Ambient Air Collection Method using Canister Passive sampling method
Flow controller
The canister is cleaned before being used for sampling, and
set to vacuum state ready for sampling. The following two
methods are used for long-period collection of ambient air.
♦ Passive sampling method Pressurized
collection method
The difference in pressure between the atmosphere and
canister are used, and the passive sampler adjusted to take
samples.
♦ Pressurization collection method
Ambient air is sent in by metal bellows pump, and the
passive sampler adjusted to take samples. Fig. 127 Ambient air collection method using canister
Tekmar-Dohrmann AUTOCanTM
Standby
Concentration temperature : -100˚C
Sample pressure check Trap preparation heating
Sample volume : 400mL
Desorption temperature : 220˚C Trap baking Trap desorption
Desorption time : 2min Sample ready Cryo trap

Analysis time wait
Cryofocus : -185˚C Trap cooling Cryo inject
Trap, MCS baking
Injection time : 2min Internal standard sample concentration
Next sample Sample pressure check
Yes
Shimadzu GCMS-QP5050A Sample concentration None
Carrier gas : He 110kPa Dry barge Trap, MCS baking
Column : AQUATIC 60m ✕ 0.25mm Cryofocusing Standby

I.D., 1µm(df)
Column temperature : 40˚C-3.5˚C/min-120˚C-6˚C/min Fig. 128 AUTOCanTM analysis flowchart
-180˚C-20˚C/min-220˚C(6min)
MIC IS 184363
ID NAME
1 Chloroethene
2 1,3-Butadiene
3 Dichloromethane
4 Acryonitrile
2
4
7 5 Chloroform
5
6 1,2-Dichloroethane
1
7 Benzene
3
8 Trichloroethene
6
8
IS Toluene-d8
9
9 Tetrachloroethene
6 8 10 12 14 16 18 20 22 (min)
Fig. 129 Nine HAPs elements (elements from the 22 priority substances that can be simultaneously analyzed) 0.1ppbv
82
Atmosphere
4.10 Automatic Analysis of Micro Amount of N2O in Atmosphere - GC
■Explanation meantime, components containing N2O are separated in

It is believed that nitrous oxide (N 2 O) exists in the main column 1, and once the quickly eluting air passes
atmosphere at approximately 300ppb. ECD is employed as through a choke column (CC2) and is discharged out of the
the detector for analysis using a gas chromatograph, and system, V2 switches to the full line, and the targeted N2O is
prolonged stable use of this detector is required for sent to main column 2 for detection by the ECD. Fig. 131
automatic analysis, which means that the following are and Fig. 132 show the chromatograms and continuous
required of a system configuration. analysis results.
1) Highly pure carrier gas References
2) Use of a well conditioned column Examples of Shimadzu System Gas Chromatograph
3) Oxygen cannot enter ECD (GC-S135)
4) Use of flow channel components that do not affect ECD Shimadzu Application News No. G161
5) Removal of non-essential components in sample
Fig. 130 shows the flow channel configuration of the ■Quantitation Limit
analysis system. Firstly, after collection of ambient air in 50ppb
sampling tube, valve V1 is switched from a full line to a
broken line to induct atmosphere components into the pre- ■Analytical Conditions
column. At the point when air, CO2 and N2O transfer to the Instrument : System including GC-14B
main column, V1 returns to the full line, and water (which Analysis time : 15 min
is an impurity) is discharged out of the system. In the Carrier gas : Argon + methane
V1 : 10way-rotary valve
V2 : 4way-rotary valve
PC : Pre Column
MC : Main Column
DC : Dummy Column
CC : Choke Column
SV : Solenoid Valve
Fig. 130 Flow channel configuration diagram
Concentration ppm
Time
Fig. 131 Chromatograms of N2O Fig. 132 Example of continuous analysis of N2O in atmosphere
83
4.10 Analysis of Non-organic Elements in Atmosphere Dust (1) - ICP-AES
Normally, an air sampler is used as an atmosphere sample Add 10mL of nitric acid, 3mL of hydrogen peroxide, 5mL
collection with a quartz filter or membrane filter used for of hydrofluoric acid to 0.2g of sample, and decomposition
collection. Collected atmosphere dust is put through a using a microwave high-speed sample decomposition
separation process with the filter, and harmful elements device. Evaporate until dry over a hotplate, then dissolve (1
analyzed using ICP-AES. A highly sensitive analyzer is + 1) with 5mL of nitric acid, and measure up to 100mL
needed as the atmosphere dust volume is extremely minute. with purified water to make analysis sample.
Here, this section introduces the inductively coupled
plasma mass spectrometer ICPS-7500, which was used for
analysis of urban atmosphere dust standard substances ■Analytical Conditions
(NIST SRM1648). The solution for the decomposition Instrument : ICPS-7500
process was inducted to the ICP, and qualitative analysis High-frequency : 27.12MHz
performed. The qualitative analysis results show the High-frequency output : 1.2kW
approximate concentration in the sample solution and the Cooling gas : Ar 14.0L/min
spectral profile. As, Ni, Mn, Cr, and Be from the priority Plasma gas : Ar 1.2L/min
substances and Pb and Cd from the regulated substances Carrier gas : Ar 0.8L/min
were qualitatively analyzed. Measuring was performed by Purge gas : Ar 3.5L/min
calibration curve, and background compensation was used Sample suction volume : 0.6mL/min
when necessary. Observation method : Side view
Observation height : 11mm
Fig. 133 Estimated concentration using qualitative analysis Fig. 134 Spectral line profile for qualitative analysis
84
Atmosphere
4.11 Analysis of Non-organic Elements in Atmosphere Dust (2) - ICP-AES
Measuring Analytical Value Guaranteed

Element Wavelength (nm) (µg/g) Performance (µg/g)
Ni 231.604 85.0 82 +
–3
As 189.042 123 115 +
– 10
Be 313.107 2.45
Mn 257.610 815 (860)
Cr 267.716 402 403 +
– 12
Pb 220.351 6500 6550 +– 80
Cd 226.502 77.0 75 +
–7
Parenthesis ( ) denote reference value.
Chart 18 Analysis results of atmosphere dust
Fig. 135 Ni calibration curve Fig. 136 As calibration curve
Fig. 137 Ni Spectral line profile Fig. 138 As Spectral line profile Fig. 139 Pb Spectral line profile
85
5. Industrial Waste
5.1 Screening of Waste Plastic Material using Horizontal ATR (1) - FTIR
■Explanation ■Device Outline

A wide range of plastic materials is used in automobiles, Figure 140 shows a diagram of the Instrument. On the top
household appliances and different kinds of containers to section of the Instrument there is a stainless steel plate
the extent that we have arrived at an era where recycling secured with a diamond prism implanted its central section.
should become compulsory. The first important step in There are two types of plate available, one with a single-
recycling plastics is the task of screening for separation reflector (diameter of 1mm) prism and the other with a
purposes of the different types of plastics that have been multi-reflector (diameter of 3mm) prism, and sample
collected. Here, the requirements are (1) instantaneous holding by pressure adjustment can also be installed.
distinction, (2) measuring regardless of shape, and (3) Furthermore, on the left and right sides of the Instrument
measuring online. At the moment, the FTIR has trouble there are purge pipe fittings that can be fitted into the
fulfilling all three requirements, however this section sample chamber wall, so that even if the sample chamber
introduces a horizontal ATR method using diamond prism lid is open, measuring can still be performed without any
with which the FTIR measures objects regardless of shape affect on the atmosphere in the chamber.
comparatively well – especially solid objects.
■Measuring Conditions
Decomposition : 8cm-1
Estimation : 100
Apodize function : Happ-Genzel
Detector : DLATGS
Fig.140 External view of instrument
86
Industrial Waste
5.1 Screening of Waste Plastic Material using Horizontal ATR (2) - FTIR
■Measuring Examples
Figures 141 to 144 show the spectral profiles of polystyrene show results for plate-shaped samples, but the FTIR can be
(PS), polyethylene (PE), polyproplyene (PP), and used to measure quite hard objects like pellets and powder
acrylonitrile butadiene styrene resin. All of these figures samples.
0.2
PS PE
0.1
ABS
ABS
0.0
0.0
4000 2500 1000 700 4000 2500 1000 700
Fig. 141 PS spectra (1/cm) Fig. 142 PE spectra (1/cm)
0.1
PP ABS
ABS 0.05
ABS
0.0
0.0
4000 2500 1000 700 4000 2500 1000 700
Fig. 143 PP spectra (1/cm) Fig. 144 ABS spectra (1/cm)
87
5.2 Analysis of Non-organic Elements in Eluate of Incineration Ash (1) - ICP-AES
■Explanation ■Analtytical Conditions

Industrial waste is usually buried after being incinerated or Device : ICPS-7500
compacted. The amount of elution from this type of waste : Ultrasonic nebulizer UAG-1
is governed by law, with elements like Cd, Hg, Pb, Cr6+, As, High frequency : 27.12MHz
Cu and Zn. Unlike tap water, wastewater and industrial Nebulizer : Coaxial type UAG-1
waste have high concentrations of coexisting elements, High-frequency output : 1.2kW 0.8kW
which makes analysis difficult. Here, the ICP spectrometry Cooling gas : Ar 14.0L/min 14.0L/min
analysis method can measure samples with minimal affect Plasma gas : Ar 1.2L/min 1.2L/min
from coexisting elements at higher sensitivity with the aid Carrier gas : Ar 1.0L/min 0.9L/min
of an ultrasound nebulizer. Purge gas : Ar 3.5L/min 3.5L/min
Sample suction volume : 2.0mL/min 2.0mL/min
References
Observation method : Side view Side view
(1) Verification method for metals, etc., contained in
Observation height : 15mm 15mm
industrial waste
(2) Japanese Industrial Standard (JIS) K0102
■Pretreatment
Under the conditions of the verification method for metals,
etc., contained in industrial waste, an elution operation was
performed. Next, 100mL of sample was taken from the test
solution, 5mL of nitric acid added, boiled over a hotplate
for approximately 10 minutes, cooled, measured up to
100mL with purified water, and stirred sufficiently.
Element Analytical Value (mg/L)

Cd <0.0005 *
Pb 0.38 *
Cr <0.0005 *
As 0.010 *
Cu 0.025
Zn 0.22
Fe 0.085
Mn 0.005
Mo 0.015
Sb 0.21 *
*: Use of ultrasonic nebulizer UAG-1
Chart 19 Incinerated ash analysis results (mg/L)
88
Industrial Waste
5.2 Analysis of Non-organic Elements in Eluate of Incineration Ash (2) - ICP-AES
Fig. 145 Pb calibration curve Fig. 146 As calibration curve
Fig. 147 P177.499nm profile Fig. 148 Mn 257.610nm profile Fig. 149 Fe 259.940nm profile
Fig. 150 Cu 327.396nm profile Fig. 151 Mo 202.030nm profile Fig. 152 Sb 206.838nm profile
89
5.3 X-ray Fluorescence Spectrometric Analysis of Industrial Waste (Sludge) - XRF
Industrial wastes like sludge and mud have their elements Grinding Conditions
analyzed so that they can be classified for burial, Instrument : Shaker mill T1-100
management or reuse. Easy, fast and thorough fluorescent Container : Tungsten carbide
x-raying is the optimum form of analysis for this work. The Time : 3min
measuring method employed is qualitative and quantitative
analysis. With this method, qualitative analysis is Pressurized Design Conditions
conducted, followed by quantitative analysis of the detected Device : Briquet machine MP-35
elements or the intensity of that fluorescent x-ray with FP Pressure : 30t
method. Standard samples are not necessary, so this method Time : 30 sec
is extremely useful when the types of analysis samples are Ring : Vinyl chloride
numerous and the marketed standard samples are few. The
following figure and chart show qualitative and quantitative ■Analtytical Conditions
analysis results as analysis examples of industrial waste. Device : Sequential x-ray fluorescence
Quantitative Lower Limit Value (target) spectrometer XRF-1700
1 to 5ppm (this differs according to element) X-ray tube : 4kW, Be thin window, Rh target
Tube voltage : 40kV
Tube ampere : 95mA
Spectrometer crystals : LiF, Ge, PET, TAP, SX-48, -58N,
-76, -14
Scanning speed : 8 degree, 4 degree, 2 degree/min
Fig. 153 Qualitative analysis of sludge
CO2 N2O5 Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl K2O CaO TiO2 Cr2O3 MnO Fe2O3 NiO CuO ZnO Br Rb2O SrO Y2O3 BaO PbO
60.73 9.99 0.17 0.85 6.97 8.89 5.72 2.12 0.064 0.31 2.81 0.16 0.012 0.038 0.90 0.004 0.018 0.055 0.002 0.001 0.019 0.000 0.18 0.002
Chart 20 Qualitative analysis value (%) of sludge
90
6. Others
6.1 Analysis of Non-agitated Soil Core Sample using Microscopic FTIR (1) - FTIR
■Explanation
To understand the existing form and distribution status of performed in the following way. The sample provided by
non-organic compounds and organic compounds contained in core sampler was wind dried, then hardened by
soil, important information - such as knowledge of the impregnation of a polyester-based resin. The sample was
features attributable to the quality and formation of the soil in then cut to a suitable size, the surface polished, and used for
question - is needed. There are almost no examples of direct measuring. The prepared sample was set on the stage of an
soil sampling using FTIR, but sampling of soil hardened infrared microscope, and measured by mapping employing a
with resin is possible. As a soil analysis method, the resin reflective method for 5✕5 mm range with aperture size 200
hardening method(1) is actively used to observe and µm square.
analyze micro structures and surface analysis, because soil
samples can be taken by core sampler and kept in a non- ■Results
agitated state. Here, this section introduces a measuring Figures 154 and 155 show the silicic acid compound from the
example of a sample prepared using this method. spectra obtained in the measuring results. Both figures
show absorption peculiarities for silicic acid compound in
the vicinity of 1100 cm-1.
Reference
(1) Kenji Tamura, Sadao Nagatsuka, Hiroshi Ohba ■Measuring Conditions
Japan Soil Nutrient Society Magazine: 166-176 (1993) Mode : Reflection
Decomposition : 8cm-1
■Pretreatment Estimate : 40
The sample used consisted of the A layer of black soil taken Apodize function : Happ-Genzel
from an eulalia plain, and the pretreatment consisted of the Detector : MCT
method depicted in reference material (1), which was Data processing device : Kramers-Kronig conv.
0.2 0.25
Abs
Abs
0.2
0.15
0.15
0.1
0.1
0.05
0.05
0.0 0.0
4000.0 2000.0 1000.0 4000.0 2000.0 1000.0
Fig. 154 Non-organic compound spectrum (1) Fig. 155 Non-organic compound spectrum (2)
91
6.1 Analysis of Non-agitated Soil Core Sample using Microscopic FTIR (2) - FTIR
If the peak is targeted, and a three-dimensional measuring 156 can be achieved. The protruding sections show the
surface is created from vertical axis values for the peak distribution of silicic acid compound.
height in a range of 800 to 1250 cm-1, the diagram in figure
Value (compensated height) range: 800 – 1250 1/cm
Fig. 156 Mapping diagram of soil core sample
92
Others
6.2 Analysis of Volatile Organic Compounds (VOC) in Soil (1) - GC/MS
■Explanation ■Analtytical Conditions

Following on from the amendments to the water quality Head Space Method
standard in tap water in December 1992 and the Head Space Sampler HS-40
environment standard for environment water in March Sample volume : 10mL+NaCl 3g
1993, a further amendment was also implemented for the Sample temperature : 60˚C
wastewater standard in February 1994. Next, based on these Heat retaining time : 30min
water standards, the environment standard related to Needle temperature : 120˚C
pollution of soil was amended in February 1994. The head Line temperature : 150˚C
space method and purge trap method are used for analysis Pressurization time : 2min
of the compounds concerned. The head space method Injection time : 0.20min
features ease of use, provides good reproducibility, can
accommodate an auto sampler, and carry over (conforming
pollutant level of device caused by concentration level of
elements) is minimal. The purge trap method allows
analysis of low-concentrate samples at high sensitivity as Shimadzu GCMS-QP5050A
samples can be concentrated using a collecting agent, which Carrier gas : He 120kPa
provides excellent sensitivity of 10 to 100 times more than Column : DB-624 60m ✕ 0.32mm I.D.,
that of the head space method. 1.8µm(df)
References Column temperature : 40˚C(2min)-10˚C/min -200˚C(2min)
(1) Drinking Water Test Method & Explanation, Japan
Water Works Association volume
(2) Environmental Water Analysis Manual, Environmental
Science Research Group volume Purge Trap Method
(3) New Wastewater Standards and Other Analysis Tekmar-Dohmann LSC3000
Methods, Environmental Science Research Group Sample volume : 5mL
volume Adsorption tube : G-2(Tenax-Silica gel)
(4) Concerning additional items for environment standard Purge time : 5min (room temp)
related to soil pollution Dry purge time : 2min
(Verdict) Central Environment Think Tank January Purge flow rate : 30mL/min
14th, 1994 Desorption time : 3min(200˚C)
Injection : 2min(200˚C)
■Pretreatment Baking : 220˚C(30min)
Creation of Sample Transfer : 150˚C
Gravel and pieces of wood exceeding a granular
diameter of 5 mm are removed from collected soil.
Sample Solution Preparation
50g of sample and 500mL of solvent (purified water:
water without VOC) are placed in a 500mL conical
flask with threaded inlet and agitator placed inside, and Shimadzu GCMS-QP5050A
the flask sealed immediately. Carrier gas : He 120kPa
Solving Out Column : DB-624 60m ✕ 0.32mm I.D.,
The prepared sample is kept at room temperature and 1.8µm(df)
atmosphere (20˚C and 1 atmosphere) while being Column temperature : 40˚C(5min)-4˚C/min-80˚C
continually stirred for 4 hours using a magnetic stirrer. -6˚C/min-140˚C-8˚C/min-180˚C
Creation of Test Solution -40˚C/min-200˚C(2min)
When the above operations are completed, let the
sample solution stand for 10 to 30 minutes, then pass it
through a membrane filter with perforation diameter of
0.45 µm to make the measuring sample solution.
93
6.2 Analysis of Volatile Organic Compounds (VOC) in Soil (2) - GC/MS
SIM
ID Name Selected Ions
TIC 89488 1 1,1-dichloroethene 96,61
2 Dichloromethane 84,86
3 trans-1,2-dichloroethene 96,61
19 4 cis-1,2-dichloroethene 96,61
6
5 Chloroform 83,85
6 1,1,1-trichloroethane 97,99
7 Tetrachloromethane 117,119
20 8 Benzene
8 78,77
9 1,2-dichloroethane 62,64
9 14 10 Trichloroethene 130,132
5 7
11 1,2-dichloropropane 63,62
17
12 Bromodichloromethane 83,85
13 cis-1,3-dichloropropene 75,110
1011 13 1516 14 Toluene 92,91
3 4 12 21
1 23
2 18 15 trans-1,3-dichloropropene 75,110
22
16 1,1,2-trichloroethene 97,99
17 Tetrachloroethene 166,164
18 Dibromochloromethane 129,127
19 m,p-xylene 106,91
20 o-xylene 106,91
6 8 10 12 14 16 18 20 22 24 26 (min) 21 Bromoform 173,175
22 p-bromofluorobenzene(IS) 174,176
23 p-dichlorobenzene 146,148
Fig. 157 SIM chromatogram (head space method) for sample with 23 Chart 21 SIM selected ions
standard elements (1µg/L) added to soil
TIC 2000000
Tetrachloroethylene
Toluene
6 8 10 12 14 16 18 20 22 24 26 28 (min)
Fig. 158 SIM chromatogram of soil (purge trap method)
94
Others
6.3 Easy Analysis of Residual MTBE in Soil (HS Method) - GC
■Explanation ■Quantitation Limit

MTBE (Methyl-t-butyl ether) is a component added mainly Approx 100ppb (concentration in soil)
to high-octane gasoline to increase the octane number. In Approx 10ppb (concentration in aqueous solution)
Japan, a decision was finalized by the major retailers of
petroleum products in the summer of 2001 to prohibit
Instrument : GC-2010 + HS40
selling high-octane gasoline containing MTBE (which is
Column : DB-VRX 60m ✕ 0.25mm I.D.
suspected of being carcinogenic) because discharges of
df = 1.4µm
such fuel would lead to the fear of soil and ground water
Column temperature : 35˚C (13 min) -13˚C/min -185˚C
pollution. The normal methods for measuring residual
(13 min) -15˚C/min -255˚C
MTBE in environment water and soil are the headspace
Injection inlet temperature : 150˚C
GC/MS and purge & trap GC/MS ones; however, for
Detector temperature : 250˚C (FID)
screening purpose, GC-FID analysis seems to be often used
Carrier gas : He 230kPa (2.2mL/min)
instead.
Injection method : Split (1:8)
References Heating temperature : 80˚C
Environment Agency bulletin No. 46, Environment Heating time : 30 min
Standards Related to Soil Pollution, 23.8.91 Injection time : 0.1 min
Amendments: 1993 environment bulletin No. 19, 1994
environment bulletin No. 25, 1995 environment bulletin
No. 19 concerning low molecular weight hydrocarbon
analysis
Shimadzu Application News No. G208
Weigh soil (50g or more) into a conical flask (stirrer chip inside) with threaded inlet.
Hydrochloric acidic blank water (pH 5.8 to 6.3) is added to make soil become 10% of weight volume ratio.
Stir for 4hr using magnetic stirrer.
Allow to stand for 30 min, then filter supernatant.
Analyze headspace gases over filtered liquid.
Fig. 159 Example of pretreatment in analysis for residual MTBE in soil
Intensity
900
800
700
600
500
400
Tol
300
m,p-Xy
o-Xy
EB
200
MTBE
100
0
-100
0 10 20 30
min
Fig. 160 Chromatogram of water extracted from gasoline-added soil
95
6.4 Analysis of Organic Tin in Seawater and Fish (1) - GC/MS, GC
■Explanation ■Analytical Conditions (GC/MS)

TBT (Tributyl Tin) and TPT (Triphenyl Tin), etc., have GC
been widely used as antifouling agents on the hulls of ships Column : DB-1 (30m ✕ 0.32mm I.D. df =
and on fishing nets to prevent adhesion of shellfish and 0.25µm)
seaweed. In 1997, Japan halted the production of paint Column temperature : 50˚C (2 min) -20˚C/min -140˚C
containing TBT, but some other nations are still using TBT, -7˚C/min -220˚C -15˚C/min -
which is a cause of seawater and marine life pollution. 310˚C
Also, TBT is suspected of having an endocrine disrupting Injection inlet temperature : 280˚C
effect. This data introduces analysis examples of the highly Carrier gas : He 40kPa
qualitatively accurate GC/MS method that can use Injection method : Splitless (sampling time 2 min)
deuterated (d labeling) compounds for internal standard Interface temperature : 300˚C
substances and the conventional GC-FPD analyzing MS
method. Scan
Reference Ionization : EI
Shimadzu Application News No. M182 Scan range : m/z 35 - 450
Shimadzu Application News No. G190 SIM
Selected Ion (m/z)
d27 : 295, 293, 316
TBT : 277, 275, 291
Tetra-BT : 291, 289
TpeT : 303, 305
d 15TPT : 366, 364
TPT : 351, 346
10g of fish 1L seawater
Extraction (1N hydrochloric acid methanolic solution)
Extraction (ethyl acetate: hexane 3:2) Extraction (ethyl acetate: hexane 3:2)
Column chromatography (cation, anion exchange resin)
Propylation (Grignard reagent: PrMgBr) Propylation (Grignard agent: PrMgBr)
Column chromatography (Florisil)
Analyte: 2mL Analyte: 2mL
GC/MS GC/MS
Fig. 161 Example of extraction method for organic tin
Fig. 162 TBT mass spectrum Fig. 163 TPT mass spectrum
96
Others
6.4 Analysis of Organic Tin in Seawater and Fish (2) - GC/MS, GC
ID : 6 mass number : 277.00

type : Target
component : TBT
retention time : 10.788

area : 44583
concentration : 1.021ppm
mass number area intensity ratio

1 291.00 18581 42
Fig. 164 SIM chromatogram using standard sample Fig. 165 SIM chromatogram for TBT in fish (sea bass)
Compound Sea Bream Sea Bass K Harbor W Harbor

TBT 0.436 µ/g 0.782 µ/g 0.173 µ/L 0.068 µ/L
TPT 0.014 µ/g 0.010 µ/g 0.019 µ/L 0.078 µ/L
Chart 22 Quantitative results for tin in fish and seawater
■Analytical Conditions (GC)

Instrument : GC-17A (FPD) Injection inlet temperature : 290˚C
Column : DB-5 30m ✕ 0.25mm I.D. df = Carrier gas : He 350kPa (1min)
0.25µm -150kPa(2.4mL/min)
Column temperature : 60˚C (1 min) -20˚C/min -140˚C Injection method : High-pressure injection, splitless
-7˚C/min -280˚C Injection volume : 3µL
6
1 3 4
2 5
10 8
10
9 1112
Compounds 7.Monophenyl Tin

mV
1.Monobutyl Tin 8.Tripentyl Tin(TPeT)

5 7
2.Dibutyl Tin(d18) 9.Diphenyl Tin(d10)
3.Dibutyl Tin 10.Diphenyl Tin
4.Tributyl Tin(d27) 11.Triphenyl Tin(d15)
5.Tributyl Tin(TBT) 12.Triphenyl Tin(TPT)
0 5 10 15 20 25 min
6.Tetrabutyl Tin(TeBT)
Fig. 166 Chromatogram of standard solution
4
Compounds
mV
1.Monobutyl Tin 7.Monophenyl Tin

6 11 12
2 8
2.Dibutyl Tin(d18) 8.Tripentyl Tin(TPeT)
5
1 23 4 10 3.Dibutyl Tin 9.Diphenyl Tin(d10)
9
7 4.Tributyl Tin(d27) 10.Diphenyl Tin
0 5.Tributyl Tin(TBT) 11.Triphenyl Tin(d15)
0 5 10 15 20 25min 6.Tetrabutyl Tin(TeBT) 12.Triphenyl Tin(TPT)
Fig. 167 Chromatogram of fish (sea bass) extraction solution
97
INDEX
DESCRIPTION PAGE DESCRIPTION PAGE
1-(2-pyridyl) piperazine 71 BaO 90
1,1,1,2-Tetrachloroethane 62 Be 85
1,1,1-trichloroethane 7,81,94 Bensulide (SAP) 14
1,1,2,2-Tetrachloroethane 62 Benzaldehyde 74
1,1,2-trichloroethane 7 Benzene 7,80,81,82,94
1,1-dichloroethane 7,61,62,81 Bis (2-Hydroxymethyl) iminotris (hydroxymethyl) methane
1,2,3-Trichloropropane 62 2,23,26,38,46,64,69
1,2-dichloroethane 7,80,81,82,94 Bisphenol A (BPA) 52
1,2-dichloropropane 7,81,94 Bis-Tris 2,23,26,38,46,64,69
1,3-Butadiene 62,82 Blue-green algae 10
17 β-Estradiol 63 Bolic acid sodium 42
1-Bromopropane 62 BPA 53
1-phenyl 7-3-methyl-5-pyarozolone 51 Br 90
2,3-Dibromopropionamide 12,13 Bromimation 12
2,3-DBPA 12,13 Bromochloromethane 62
2,4-Dinitrophenylhydrazine 74 Bromodichloromethane 7,62,94
2,4-TDI 71 Bromoform 7,94
2,6-TDI 71 Bromomethane 62
2-BPA 12 Butamifos 14
2-Bromopropane 62 Butyraldehyde 74,76
2-Bromopropeneamide 12 C-18 cartrige 63
2-Methylisoborneol 8,9,10,11 Ca 16,30,84
2MIB 8,9,10,11 Ca2+ 3,4,24,25,27,29,36,39,41,65,67
3,3’dichloro-4,4’-Diaminodiphenylmethane 71 calcium ion 3,4,24,25,27,29,36,39,41,65,67
4-Pyridinecarboxylic acid pyrazolone method 50 Canister 82
ABS 87 CaO 90
Acephate 14 Captan 14
Acetaldehyde 74,76 carbon molecular sieves 79
Acetone 74 CAT 14
Acetonitrile 53,74,75,77 Cation 3,4,24,25,27,29,36,37,41,65,67
Acrolein 74,76 Cd 16,17,18,19,32,34,85,88
Acrylamid 12,13 Chlomethane 62
Acrylonitrile 80 Chloramine T 51
Acrylonitrile butadiene styrene resin 87 Chloride (ion) 1,2,5,22,23,26,28,35,38,40,43,64,66,69,70
Actinomycetes 10 Chlorobenzene 62
ADI 15 Chloroethane 62
agrochemicals used at golf course 14 Chloroform 7,80,81,82,94
Al 16,17,18,33,84 Chloromethane 62
Al2O3 90 Chlorothalonil 14
Aldehyde 73 Chlorpyrifos 14
Alkyl Mercury 54 chrome 16,18,32,33,34,84,85,88
Allyl chloride 62 cis-1,2-dichloroethene 7,94
ammonium ion 4,24,25,29,36,39,41,65 cis-1,3-dichloropropene 7,94
Anions 1,2,5,22,23,26,28,35,38,40,43,44,64,66 Citric acid ammonium 42
Apodize function 86 Cl– 1,2,5,22,23,26,28,35,38,40,43,64,66,69,70
Aquatic 62,82 Clean Air Act 74
As 16,18,19,20,33,85,88,89 CO2 90
Asahipak NH2P-50 44 Colorimeric method 16
Atomic absorption method 20,21,30,32 core sampler 91,92
B 16,33,84 Cr 16,18,32,33,34,84,85,88
Ba 16 CrO3 90
Back ground correction 30 Cu 16,17,18,33,88,89
98
INDEX
CuO 90 Ethylenediaminetetraacetic acid (EDTA) 15
Cyanogen Chloride 50 Ethylenneimine 71
cyanogen compounds 50 Ethylmercury chloride 54
cyanogen ion 50 Eutrophication 31
Cycropentane 62 Evaluating tap water chemicals 12
CyDTA 15 F– 1,2,3,22,23,26,28,40,46,47,66
D2 30 FAO/WHO 15
D2 method 30 Fe 16,18,84,88,89
DB-1 14,58,59,75,76,80,95 Fe2O3 90
DB-1701 8 Fenitrothion (MEP) 14
DB-5 11,96 Fishing net 96
DB-5H 63 Flame atomic absorption method 30
DB-624 6,60,92 Florisil/C18 cartridge 63
DB-VRX 68,94 Fluorine (Ion) 1,2,3,22,23,26,28,40,46,47,66
DB-WAX 12 Fluorometric detector 42
Diazinon 14 Flutolanil 14
Diazinon oxone 14 Formaldehyde 42,74,76
diazotization coupling absorptiometry 71 FPD 58,97
Dibromochloromethane 7,62,94 FTD 76
Dibutyl Tin 97 Furnace method 20,21
Dichloromethane 7,15,80,81,93 GC 12,13,54,55,56,57,58,59,68,76,77,83,95,96,97
Diffusive separation method 46 GCMS 6,7,8,9,10,11,12,13,14,15,60,61
Dinitrophenylhydrazine 74 62,63,80,81,82,83,93,94,96,97
Diphenylamine 76 Geosmin 8,9,10,11
Dipicolinic acid 25 GPC column 63
Dithiopyr 14 Gradient 74
DLATGS 86 Graphite carbon black 79
DNPH 74 Guide line 15
DNPH derivatives 74 H type ion replacement cartridge column 47
DNPH silica gel 77 H2O2 69
ECD 12,54,55,56,57 Halogen compounds 13
EDTA 15 HCHO 78
EDTA2Na 53 HCl 69
–
Effulent standards 31 HCO3 5,28,35,66
Ehynyl estradiol 63 Head Space 60,61,93,94,95
Electric conductibity detector 1,2,3,4,5,22,23,24,25,26,27 Hexaaldehyde 74
28,29,35,36,37,38,39,43,46,47,64,65,66,67,69 Hexamethyldisiloxane 47
Electro-thermal atomization 20,21 High pressure boiling instrument sterilizer 31
Eluate of incineration ash 88,89 Hot spring water 35,36,37
Endocrin disruptor compound 52 HPLC 42,45,48,49,50,51,71,72,73,74,75
Endocrine disruptor compound 52 HR-Thermon-HG 55
Environment standards 31 Hulls of ships 96
EPA 74 Hydroxy methansulfonic acid 42
EPN 58 i-Butylaldehyde 76
ESA Coulochem II guard cell 0.6V 53 IC method 3
Estradiol 63 IC-MA3-1 28,29,40,41,66,67
Estriol 63 ICP emission spectroscopic analysis method
Estron 63 16,17,18,19,83,84,88,89
Ethyl acetate 12,13 ICP mass spectrometry (ICP-MS) 33,34
Ethyl beinzene 62 ICP-AES 16,17,18,19,84,85,88,89
Ethylbenzene 62 ICP-MS 33,34
Ethylenediamine 37 Inductively coupled plasma mass spectrometer 33,34
99
INDEX
Inorganic anion 22,26 Mineral water 18,19
Inorganic ion 22,26 Mn 16,18,33,84,85,88,89
Interference control agent 30 MnO 90
Ion Chromatograph 1,2,3,4,5,22,23,24,25,26,27,28,29 Mo 18,19,84,88
35,36,37,38,39,43,46,47,64,65,66,67,69 Monobutyl Tin 97
ion electrode method 50 Monophenyl Tin 97
ion exchenge cartridge column 77 MTBE 95
Iprodione 14 Musty Smelling Components 8,9
Isobutane 13 Myclocystine 48
isofenphos 14 Myclocystine LR 48
isoindole 42 Myclocystine RR 48
Isopuothioram 14 Myclocystine YR 48
isoxathion 14 N2O 83
isoxathion oxione 14 N2O5 90
I-Valealdehyde 76 Na 16,84
JIS K0102 31 Na+ 3,4,24,25,27,29,36,39,41,65,67
JIS K0303 73 Na2O 90
K 16,84 NaHCO3 1,22
K+ 3,4,24,25,27,29,36,39,41,65,67 NaOH 69
K2O 90 Napropamide 14
ketonic products 73 n-Butylaldehyde 74,76
KT2-2322 31 NCI 13
La 30 Negative chemical ionization 13
Lake water 26,27 NH4+ 4,24,25,29,36,39,41,65
L-Cysteine/Sodium acetate 55 NHClO4 47
L-Cysteine-hydrate 55 n-Hexane 62
Lithium ion 24,25 Ni 18,33,85
LSC3000J 6,8,92 NiO 90
m,p-xylene 7,81,94 NIST 30
Magnesium ion 3,4,24,25,27,29,39,41,67 Nitrate 16,20,21,32,33,36
Mapping 92 Nitrate ion 1,2,5,22,23,26,28,35,38,40,43,44,64,66,69,70
Mask interference 30 Nitrates 1,64
Matorix modifier 20,21 Nitrites 1
MBPMC 14 Nitrous oxide (N2O) 83
MEK 76 NO3– 1,2,5,22,23,26,28,35,38,40,43,44,64,66,69,70
Membrane filter 1,2,3,4,5,2,23,24,25,26,27,28,29,35,36 Non-suppressor system 3,24
37,38,39,43,44,45,46,47,64,65,66,67,69,70 NOX 69
MEP oxione 14 n-Valeraldehyde 76
Mepronil 14 OPA 42
Metalaxyl 14 Organictin 96,97
Methcrolein 74 orthophthalaldehyde 42,45
Methyl Demeton 58 OV-1 56
Methyl dymron 14 Oxalic acid 4,25,27
Methyl Parathion 58 o-xylene 7,81,94
Methyl-butylether 62 ozone scrubber 77
Methylmercury chloride 54 P2O5 90
Metyl-t-buthlether 62 Parathion 58
Mg 16,30,33 Passive sampling method 82
Mg+ 3,4,24,25,27,29,39,41,67 Pb 16,18,19,21,33,34,84,85,88,89
MgO 90 PBB reaction liquid 63
MIBK 76 PbO 90
Microwave high-speed sample decomposition device 84 p-bromofliorbenzene 7,94
100
INDEX
p-bromofluobenzene 7,61,92 Silica gel column Chromatogram 57
PCB 56 Simazine (CAT) 14
p-dichlorobenzene 7,94 SiO2 90
PDMS/DVB 11 SO3 90
PE 87 SO42– 1,2,5,6,22,23,26,28,35,38,40,43,64,66,69,70
Pencycuron 14 Sodium acetate trihydrate 55
Pendimethalin 14 Sodium carbonate 1,22
PFB derivatization 63 Sodium Citrate 42,45
Phosphoric ion 23,28,64,66 Sodium hydrogen carbonate 1,22
Phthalic acid 43,64 Sodium hyposulfite 13
p-hydroxybenzoic acid 2,23,26,38,46,69 Sodium ion 3,4,24,25,27,29,36,39,41,65,67
PIA-1000 28,29,40,41,66,67 Sodium perchlorate 44
Plant plankton 31 Sodium sulfate 55
Polyethylene (PE) 87 Solgell 15
Polyethylene (PS) 87 Solid -phase extraction 1
Polypropylene (PP) 87 SOX 69
Polyurethane foam 71 SPME 11
Post column derivative method 50 Sr 16,84
Potassium bromate 12,13 SrO 90
Potassium ion 3,4,24,25,27,29,36,39,41,65,67 Standard substances in rever water JAC031 33
PP 87 Standard substances in rever water JAC032 33
Propionaldehyde 74,76 STR ODS-II 48,74
Propyzamide 14 Styrene 81
PS 87 Sulfate ion 1,2,5,6,22,23,26,28,35,38,40,43,64,66,69,70
Purge & trap method 8,9,92,93 Sulfurous acid 42
Pyributycarb 14 suppressor system 22
Pyridaphenthion 14 surrogate 63
Pyridine-4-carboxylic amid 51 Tartaric acid 37
Pyridine-pyrazolone method 50 TBT 96
Rankine 42 TDI 71
Rankine method 42 Tenax 6,9
Rb2O 90 Tenax-Silica gel 92
Red tide 31 Terbucarb 14
red water 31 Tetrabutyl Tin 97
Rtx-5ms 10 Tetrachloroethene 7,80,81,82,94
S 16,84 Tetrachloromethane 7,94
SAP 14 The American Environmental Protection Agency (EPA) 74
Separate screen test solution 57 Thermon-HG 54
Sep-Pak Plus tC18 49 THF 74
Shim-pack AMINO-Na 51 Thiocyanic acid 50
Shim-pack IC-A1 35,43,64 Threshold value 8
Shim-pack IC-A3 2,23,26,38,46,69 TiO2 90
Shim-pack IC-A3 (S) 5,28,40,66,70 TMS 63
Shim-pack IC-C1 36,37,65 TMS derivatization 63
Shim-pack IC-C3 4,25,27,39 TMS imidazole 63
Shim-pack IC-C3 (S) 29,41,67 TNP 14
Shim-pack IC-SA2 1,22 TO Method-11 74
Shim-pack IC-SC1 3,24 Toluene 7,81,82,94
Shim-pack ISC-07/S1504Na 45 Toluene-d8 81,82
Shim-pack SPC-RP3 53 Tolylenediisocyanate 71
Shim-pack VP-ODS 53 Total nitrite plus nitrate nitrogen 1
Si 16 Total nitrogen 31
101
INDEX
Total phosphorus 31
TPT 96
trans-1,2-dichloroethene 7,94
trans-1,3-dichloropropene 7,94
Tributyl Tin 97
Tributyltin (TBT) 96
Trichloroethene 7,80,81,82,94
Triclophyrbutosyethyl 14
Triclorphos-methyl 14
Triethylamine 12,13
Triphenyl Tin 97
Triphenyltin (TPT) 96
UAG-1 18,88
Ultrasonic nebulizer 16,18,88
UV 31,78
Vacuum flask method 70
Valeraldehyde 74,76
Vinyl chloride 62
VOC 6,7,60,61,62,79,80,81,82,92,93
Volatile organic compounds 6,7,60,61,62,79
80,81,82,92,93
X-ray Fluorescence Spectrometric Analysis 90
XRF 90
Y2O3 90
ZB-WAX 13
Zn 16,33
ZnO 90
α-Estradiol 63
β-Estradiol 63
102
SHIMADZU CORPORATION. International Marketing Division
3. Kanda-Nishikicho 1-chome, Chiyoda-ku, Tokyo 101-8448, Japan Phone: 81(3)3219-5641 Fax. 81(3)3219-5710
Cable Add.:SHIMADZU TOKYO
SHIMADZU SCIENTIFIC INSTRUMENTS, INC.
7102 Riverwood Drive, Columbia, Maryland 21046, U.S.A.
Phone: 1(410)381-1227 Fax. 1(410)381-1222 Toll Free: 1(800)477-1227
SHIMADZU DEUTSCHLAND GmbH
Albert-Hahn-Strasse 6-10, D-47269 Duisburg, F.R. Germany Phone: 49(203)7687-0 Fax. 49(203)766625
SHIMADZU (ASIA PACIFIC) PTE LTD.
16 Science Park Drive #01-01 Singapore Science Park, Singapore 118227, Republic of Singapore
Phone: 65-778 6280 Fax. 65-779 2935
SHIMADZU SCIENTIFIC INSTRUMENTS (OCEANIA) PTY. LTD.
Units F, 10-16 South Street Rydalmere N.S.W. 2116, Australia
Phone: 61(2)9684-4200 Fax. 61(2)9684-4055
SHIMADZU DO BRASIL COMERCIO LTDA.
Rua Cenno Sbrighi, 25, Agua Branca, Sao Paulo, CEP 05036-010, BRAZIL
Phone: (55)11-3611-1688 Fax. (55)11-3611-2209
SHIMADZU (HONG KONG) LIMITED
Suite 1028 Ocean Center, Harbour City, Tsim Sha Tsui, Kowloon HONG KONG
Phone: (852)2375-4979 Fax. (852)2199-7438
Overseas Offices
Istanbul, Beijing, Shanghai, Guangzhou, Shenyang, Chengdu, Moscow
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Analysis Guidebook: Environmental Analyses

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C180-E058A

Fig. 1 Analysis example of tap water

■Pretreatment ■Analytical Conditions

Fig. 2 Analysis example of tap water

Fig. 3 Analysis example of Tap water

■Pretreatment ■Analytical Conditions

Fig. 5 Analysis example of tap water (PIA-1000)

■Explanation ■Analytical Conditions

Fig. 6 Measuring example of 0.1 µg/L added water

ID Name SIM Selected Ions ID Name SIM Selected Ions

Fig. 7 Purge & trap GC/MS system

■Explanation ■Analytical Conditions

Fig. 8 Analysis example of musty odor 3.0ppt Fig. 9 Calibration curve

CH3 CH3 CH3

Fig. 10 Structures of 2-MIB and geosmin

Fig. 11 Principle diagram of purge & trap method

■Explanation ■Analytical Conditions

Fig. 12 SIM chromatogram

Fig. 13 Calibration curve (0.001 to 0.050µg/L)

■Explanation not use organic solvents required by conventional solid-

(1)2-MIB intensity intensity (2)Geosmin intensity intensity

50000 400000 60000 600000

45000 55000 550000

Fig. 14 SIM chromatograms

(1)2-MIB [*10^6] (2)Geosmin [*10^6]

# Concentration (µg/L) Area # Concentration (µg/L) Area

Fig. 15 Calibration curves (0.001 to 0.050µg)

10.0 10.0 Acrylamide Br

■Explanation ■Analytical Conditions

Sample Sulfuric acid (1 +5) pH no more than 1

Derivatization Potassium bromate solution

Solvent extraction Ethyl acetate O

Fig. 18 Pretreatment flow Fig. 19 Derivatization reaction

Retension time: 15.8 (Scan #:216)

■Explanation ■Analytical Conditions

Fig. 25 Total ion chromatogram Chart 2 Monitor mass list

#: 1 Retention time: 15.4 (Scan #: 167)

Desiccate by N2 gas Fig. 27 EDTA mass spectrum

Leave for 1hr at 80°C

Shaking & centrifuging

Fig. 28 CyDTA (IS) mass spectrum

Fig. 26 Pretreatment flow

5,437 174.10 176,159 402.15

15.0 16.0 17.0 18.0 min

Chart 3 Tap water analysis results (µg/mL)

Fig. 31 Cd calibration curve

Fig.32 Al calibration curve

Fig. 33 Profile of Al 167.079nm Fig. 34 Profile of Cd 228.802nm Fig. 35 Profile of Cu 324.754nm

Chart 4 Analysis results for mineral water (ng/mL)

Fig. 36 Pb calibration curve

Fig. 37 As calibration curve

Fig. 38 Peak profile of Mo Fig. 39 Peak profile of Cd Fig. 40 Peak profile of Pb

■Explanation ■Sample Adjustments and Measuring Method

Chart 5 As measuring conditions Chart 6 As analysis results

Calibration curve (calibration curve #: 01) Tap water + 2ppb: SPIKE

Abs 0.200 Conc Abs 0.000

Set concentration Concentration Absorbance BG Actual concentration %R

0.050 2.0000 0.0905 Set concentration Concentration Absorbance BG

Set concentration Concentration Absorbance BG Actual concentration %R

Fig. 41 As calibration curve Fig. 42 Peak profiles at time of As analysis

■Explanation ■Sample Adjustments and Measuring Method

Chart 7 Pb measuring conditions Chart 8 Pb analysis results

River water without addition: UNK

(1)2-MIB [10^6] (2)Geosmin [10^6]