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Environmental Analyses

Shimadzu Analysis Guidebook

C180-E058C

Index

2.16 Analysis of Sulfurous Acid Ions in Rainwater - LC ------------------------------------- 722.17 Analysis of Anions in Snow Water - Ion Chromatograph ----------------------------- 732.18 Analysis of Anions in Seawater - LC ----------------------------------------------------- 742.19 Analysis of Ammonia Ions in Seawater - LC -------------------------------------------- 752.20 Analysis of Inorganic Components in Seawater (1) - ICP-AES ----------------------- 76

Analysis of Inorganic Components in Seawater (2) - ICP-AES ----------------------- 772.21 Analysis of Inorganic Components in Underground Water -ICP-AES --------------- 782.22 Analysis of Microcystins in Blue-green Algae (1) - LC -------------------------------- 79

Analysis of Microcystins in Blue-green Algae (2) - LC -------------------------------- 802.23 High-Sensitivity Analysis of Bisphenol A in Environment Water (1) - LC ----------- 81

High-Sensitivity Analysis of Bisphenol A in Environment Water (2) - LC ----------- 822.24 Analysis of Alkyl Mercury Compound (1) - GC ----------------------------------------- 83

Analysis of Alkyl Mercury Compound (2) - GC ----------------------------------------- 842.25 Analysis of Microcystins using GC/MS - GC/MS --------------------------------------- 852.26 Analysis of Volatile Organic Compounds (VOCs) (P/T Method) - GC/MS ----------- 862.27 Reducing Time for the Analysis of VOCs in Water using Purge&Trap GC/MS - GC/MS ----- 872.28 Analysis of Estradiol - GC/MS ------------------------------------------------------------ 88

3. Wastewater

3. 1 Analysis of Anions in Wastewater - Ion Chromatograph ------------------------------ 893. 2 Analysis of Volatile Organic Compounds (VOCs) in Wastewater - GC --------------- 903. 3 Analysis of Inorganic Components in Wastewater (1) - ICP/MS --------------------- 91

Analysis of Inorganic Components in Wastewater (2) - ICP/MS --------------------- 92

4. Atmosphere4. 1 Analysis of Acidic Substances in Exhaust Gas - Ion Chromatograph ---------------- 934. 2 Analysis of Tolylenediisocyanate (TDI) in Work Environment Monitoring (1) - LC -------- 94

Analysis of Tolylenediisocyanate (TDI) in Work Environment Monitoring (2) - LC -------- 954. 3 Analysis of Aldehyde / Ketonic products in Exhaust Gas - LC ------------------------ 964. 4 Analysis of Aldehyde / Ketonic products in Room Atmosphere (1) - LC ------------ 97

Analysis of Aldehyde / Ketonic products in Room Atmosphere (2) - LC ------------ 984. 5 Analysis of Aldehydes in Atmosphere (1) - GC ----------------------------------------- 99

Analysis of Aldehydes in Atmosphere (2) - GC --------------------------------------- 1004. 6 Analysis of Formaldehyde in Room Atmosphere - UV ------------------------------- 1014. 7 Analysis of Volatile Organic Compounds (VOCs) in Atmosphere (1) - Solid-phase Adsorption & Thermal Desorption GC/MS --- 102

Analysis of Volatile Organic Compounds (VOCs) in Atmosphere (2) - Solid-phase Adsorption & Thermal Desorption GC/MS ---- 1034. 8 Analysis of Volatile Organic Compounds (VOCs) in Atmosphere (1) - Container Collection Method GC/MS ---- 104

Analysis of Volatile Organic Compounds (VOCs) in Atmosphere (2) - Container Collection Method GC/MS ---- 1054. 9 Automatic Analysis of Micro Amount of N2O in Atmosphere - GC ----------------- 1064.10 Analysis of Inorganic Components in Atmospheric Dust - ICP-AES --------------- 1074.11 Analysis of Inorganic Components in Atmospheric Dust (1) - ICP/MS ------------ 108

Analysis of Inorganic Components in Atmospheric Dust (2) - ICP/MS ------------ 1094.12 Analysis of Inorganic Components in Fly Ash (1) - ICP/MS ------------------------- 110

Analysis of Inorganic Components in Fly Ash (2) - ICP/MS ------------------------- 111

5. Industrial Waste5. 1 Analysis of PCBs in Insulating Oil - GC ------------------------------------------------ 1125. 2 Measurement of Metals in Industrial Waste - AA ------------------------------------- 1135. 3 Screening of Waste Plastic Material using Horizontal ATR (1) - FTIR ------------- 114

Screening of Waste Plastic Material using Horizontal ATR (2) - FTIR ------------- 1155. 4 Analysis of Inorganic Components in Fly Ash - ICP/MS ----------------------------- 1165. 5 Determination of Asbestos in Admixture for Mortar - TA ---------------------------- 1175. 6 Analysis of Asbestos - XRD ------------------------------------------------------------- 1185. 7 X-ray Fluorescence Spectrometric Analysis of Industrial Waste (Sludge) - XRF ---- 119

6. Others6. 1 Easy Analysis of Residual MTBE in Soil (HS Method) - GC ------------------------- 1206. 2 Analysis of Organic Tin in Seawater and Fish (1) - GC/MS, GC --------------------- 121

Analysis of Organic Tin in Seawater and Fish (2) - GC/MS, GC --------------------- 1226. 3 Analysis of Volatile Organic Compounds (VOCs) in Soil (HS, P/T Method) (1) - GC/MS -- 123

Analysis of Volatile Organic Compounds (VOCs) in Soil (HS, P/T Method) (2) - GC/MS -- 1246. 4 Analysis of Metals in Soil - AA ---------------------------------------------------------- 1256. 5 Analysis of Chromium in Soil using Atomic Absorption Spectrometry - AA ------ 1266. 6 Analysis of Non-agitated Soil Core Sample using Microscopic FTIR (1) - FTIR -- 127

Analysis of Non-agitated Soil Core Sample using Microscopic FTIR (2) - FTIR -- 1286. 7 Analysis of Inorganic Components in Soil (1) - ICP/MS ----------------------------- 129

Analysis of Inorganic Components in Soil (2) - ICP/MS ----------------------------- 1306. 8 Analysis of Inorganic Components in Pond Sediment - ICP-AES ------------------ 1316. 9 Analysis of Inorganic Components in Sewage Sludge (1) - ICP-AES, ICP/MS ---- 132

Analysis of Inorganic Components in Sewage Sludge (2) - ICP-AES, ICP/MS ---- 133

W

1. Drinking Water1. 1 Analysis of Anions in Tap Water (1) - Ion Chromatograph ----------------------------- 1

Analysis of Anions in Tap Water (2) - Ion Chromatograph ----------------------------- 21. 2 Analysis of Cations in Tap Water (1) - Ion Chromatograph ---------------------------- 3

Analysis of Cations in Tap Water (2) - Ion Chromatograph ---------------------------- 41. 3 Analysis of Carbofuran, Methomyl, and Carbaryl - LC ---------------------------------- 51. 4 Analysis of Diquat - LC ------------------------------------------------------------------------ 61. 5 Analysis of Iprodione, Asulam, Thiophanate-methyl, and Siduron - LC ------------------- 71. 6 Analysis of Iminoctadine Triacetate - LC ------------------------------------------------- 81. 7 Analysis of Glyphosate - LC ----------------------------------------------------------------- 91. 8 Analysis of Controlled Pesticides in Tap Water using Online Solid-Phase Extraction LC/MS - LC/MS --- 101. 9 Simultaneous Analysis of Pesticides Covered by the Water Quality Control Standards using LC/MS (1) - LC/MS --- 11

Simultaneous Analysis of Pesticides Covered by the Water Quality Control Standards using LC/MS (2) - LC/MS --- 12Simultaneous Analysis of Pesticides Covered by the Water Quality Control Standards using LC/MS (3) - LC/MS --- 13

1.10 Simultaneous Analysis of Pesticides Covered by the Water Quality Control Standards using GC/MS (1) - GC/MS --- 14Simultaneous Analysis of Pesticides Covered by the Water Quality Control Standards using GC/MS (2) - GC/MS --- 15

1.11 Analysis of Bromate by Post-Column Ion Chromatography (1) - LC ---------------- 16Analysis of Bromate by Post-Column Ion Chromatography (2) - LC ---------------- 17

1.12 Speciation Analysis of Cyanogen Compounds by Post-Column Ion Chromatography (1) - LC --- 18Speciation Analysis of Cyanogen Compounds by Post-Column Ion Chromatography (2) - LC --- 19

1.13 Analysis of Nitrite Nitrogen - Ion Chromatograph -------------------------------------- 201.14 Analysis of Chlorite, Chlorate, and Chlorine Dioxide - Ion Chromatograph --------- 211.15 Analysis of Isocyanuric Acid - LC ------------------------------------------------------------ 221.16 Analysis of Anionic Surfactants - LC ---------------------------------------------------- 231.17 Analysis of Microcystins using Online Solid-Phase Extraction LC/MS - LC/MS ---- 241.18 Analysis of Chloral Hydrate and Haloacetonitriles (1) - GC/MS ---------------------- 25

Analysis of Chloral Hydrate and Haloacetonitriles (2) - GC/MS ---------------------- 261.19 Solvent Extraction and GC/MS Analysis of Haloacetic Acids in Water - GC/MS ---- 271.20 Solid-Phase Extraction, Derivatization, and GC/MS Analysis of Phenols in Water - GC/MS ---- 281.21 Solid-Phase Extraction and GC/MS Analysis of 1,4-Dioxane in Water - GC/MS ---- 291.22 Headspace Analysis of 1,4-Dioxane in Water - GC/MS -------------------------------- 301.23 Simultaneous Analysis of 1,4-Dioxane and VOCs in Water using Purge&Trap GC/MS - GC/MS --- 311.24 Analysis of the Components Controlled under the Waterworks Law with a Single Column (1) - GC/MS --- 32

Analysis of the Components Controlled under the Waterworks Law with a Single Column (2) - GC/MS --- 33Analysis of the Components Controlled under the Waterworks Law with a Single Column (3) - GC/MS --- 34

1.25 Analysis of Volatile Organic Compounds (VOCs) in Tap Water (1) - Purge & Trap GC/MS -- 35Analysis of Volatile Organic Compounds (VOCs) in Tap Water (2) - Purge & Trap GC/MS -- 36

1.26 Simultaneous Analysis of Monitored VOCs in Water using Purge&Trap GC/MS - GC/MS --- 371.27 Analysis of Musty Smelling Components in Tap Water (P/T Method) (1) - GC/MS ---- 38

Analysis of Musty Smelling Components in Tap Water (P/T Method) (2) - GC/MS ---- 391.28 Analysis of Musty Smelling Components in Tap Water (HS Method) - GC/MS ---- 401.29 Analysis of Musty Smelling Components in Tap Water (SPME Method) - GC/MS ---- 411.30 Headspace–GC/MS Analysis of Fishy Smelling Components in Water - GC/MS --- 421.31 Analysis of Acrylamide in Water (1) - GC, GC/MS ------------------------------------- 43

Analysis of Acrylamide in Water (2) - GC, GC/MS ------------------------------------- 441.32 Analysis of Ethylenediamine Tetraacetic Acid (EDTA) - GC/MS ---------------------- 451.33 TOC Analysis of Chlorinated Isocyanuric Acid - TOC ---------------------------------- 461.34 TOC Analysis of Leachate from Water Pipes - TOC ------------------------------------ 471.35 TOC Analysis of Mineral Water and Raw Water - TOC --------------------------------- 481.36 Direct Analysis of As in Tap Water and River Water - AA ----------------------------- 491.37 Direct Analysis of Pb in Tap Water and River Water - AA ----------------------------- 501.38 Analysis of Inorganic Components in Water - ICP/MS -------------------------------- 511.39 Analysis of Nonionic Surfactants by Solid-Phase Extraction – Absorption Spectrophotometry - UV --- 52

2. Environment Water2. 1 Analysis of Anions in River Water (1) - Ion Chromatograph -------------------------- 53

Analysis of Anions in River Water (2) - Ion Chromatograph -------------------------- 542. 2 Analysis of Cations in River Water (1) - Ion Chromatograph ------------------------- 55

Analysis of Cations in River Water (2) - Ion Chromatograph ------------------------- 562. 3 Analysis of Anions in Lake Water - Ion Chromatograph ------------------------------ 572. 4 Analysis of Cations in Lake Water - Ion Chromatograph ------------------------------ 582. 5 Analysis of Golf Course Pesticides (1) - LC --------------------------------------------- 59

Analysis of Golf Course Pesticides (2) - LC --------------------------------------------- 602. 6 Analysis of Calcium and Magnesium in River Water - AA ----------------------------- 612. 7 Analysis of Zinc in River Water - AA ----------------------------------------------------- 622. 8 Direct Analysis of Cd and Cr in Seawater - AA ----------------------------------------- 632. 9 Measurement of Total Phosphorus in Water Solution by Absorption Spectrophotometry- UV --- 642.10 Analysis of Inorganic Components in River Water (1) - ICP-AES -------------------- 65

Analysis of Inorganic Components in River Water (2) - ICP-AES -------------------- 662.11 Analysis of Inorganic Components in River Water- ICP/MS -------------------------- 672.12 Analysis of Cations in Hot Spring Water - Ion Chromatograph ----------------------- 682.13 Speciation Analysis of Arsenic in Hot Spring Water - AA ----------------------------- 692.14 Analysis of Anions in Rainwater - Ion Chromatograph -------------------------------- 702.15 Analysis of Cations in Rainwater - Ion Chromatograph ------------------------------- 71

1

1. Drinking Water1.1 Analysis of Anions in Tap Water (1) - Ion Chromatograph

■ ExplanationIn December 1992 amendments were made to theMinisterial ordinance related to drinking water qualitystandard, the reference values for fluorine, chlorine andtotal nitrite plus nitrate nitrogen were set, and the ionchromatograph method was adopted as the analysis method.Also, in 2000, a monitoring item for nitrite nitrogen (5 ppb)was newly added to the ordinance. In addition to the abovesubstances, the ion chromatograph also can simultaneouslyanalyze phosphate ions and sulfate ions.

■ PretreatmentFiltering through a membrane filter (0.45 µm) for ionchromatography

■ Analytical Conditions

min0 5 10

µS/c

m

5

10

01

2

3

4

5

µS/c

m

10 min

0.2

0

1

2

3

Fig. 1.1.1 Analysis example of tap water

■ Peaks

1 F–

0.083 ppm

2 Cl–

14.0 ppm

3 NO3–

0.289 ppm

4 SO42 – 14.6 ppm

Instrument

ColumnMobile Phase

Flow RateTemperatureDetection

: Ion Chromatograph (Suppressor System)

: Shim-pack IC-SA2 (250 mmL. × 4.0 mm I.D.) : 12 mM Sodium Hydrogen Carbonate

(NaHCO3)0.6 mM Sodium Carbonate (Na2CO3)

: 1.0 mL/min: 30˚C: Electric Conductivity Detector

2

0 10 (min)

12

4

3 5

1.1 Analysis of Anions in Tap Water (2) - Ion Chromatograph



Fig. 1.1.2 Analysis example of tap water

■ Peaks

1 CO32 – (35 mg/L)

2 F–

(0.071 mg/L)

3 C1–

(10.1 mg/L)

4 NO3–

(1.2 mg/L)

5 SO42 – (17.8 mg/L)

Instrument

ColumnMobile Phase

Flow RateTemperatureDetection* Bis-Tris

: Ion Chromatograph (Non-Suppressor System)

: Shim-pack IC-A3 (150 mmL. × 4.6 mm I.D.): 8.0 mM p-Hydroxybenzoic Acid

3.2 mM Bis-Tris*: 1.5 mL/min: 40˚C: Electric Conductivity Detector: Bis (2-Hydroxyethyl) Iminotris

(Hydroxymethyl) Methane

3

1.2 Analysis of Cations in Tap Water (1) - Ion Chromatograph

■ ExplanationSodium, and calcium and magnesium, etc., as items related toproperties that tap water have are defined as test subjectsfor hardness in the Japanese water quality standard. The2001 edition of the Drinking Water Test Method introduces theion chromatograph (IC) method as an anion analysismethod. In addition to the above substances, the IC methodalso is capable of simultaneously analyzing lithium ion,potassium ion and ammonium ion. The acidic operatingcondition of the non-suppressor system is suitable forseparating and detecting ammonium ion.

ReferenceLC talk, Volume 42 (p6-7)



min0 5 10

µS/c

m

10

20

30

0

1

2

3

4

Fig. 1.2.1 Analysis example of Tap water

■ Peaks

1 Na+

18.057 ppm

2 K+

3.434 ppm

3 Mg2 + 4.455 ppm

4 Ca2 + 23.308 ppm

Instrument

ColumnMobile PhaseFlow RateTemperatureDetection


: Shim-pack IC-SC1 (150 mmL. × 4.6 mm I.D.): 3.0 mM Sulfuric Acid: 1.2 mL/min: 30˚C: Electric Conductivity Detector

4

1.2 Analysis of Cations in Tap Water (2) - Ion Chromatograph



Fig. 1.2.2 Analysis example of sample with addition of 10ppb of NH4+ in tap water

Instrument


: Ion Chromatograph(Non-Suppressor System)

: Shim-pack IC-C3 (100 mmL. × 4.6 mm I.D.): 2.0 mM Oxalic Acid: 1.2 mL/min: 40˚C: Electric Conductivity Detector

■ Peaks

1 Na+

8.25 ppm

2 NH4+

0.01 ppm

3 K+

1.66 ppm

4 Mg2 + 2.22 ppm

5 Ca2 + 11.85 ppm

(min)

1.3 Analysis of Carbofuran, Methomyl, and Carbaryl - LC

■ ExplanationIn the 2001 revision of the Japanese Drinking Water TestMethod, methomyl and carbaryl in addition to carbofuran,were added to test items for N-methycarbamate pesticides. This section describes examples of analysis by post-columnfluorescent derivatization of these three components ––carbofuran, methomyl, and carbaryl. Carbofuran,methomyl, and carbaryl can be detected at high sensitivityusing post-column derivatization with o-phthalaldehyde(OPA) as the reaction reagent. With this method, the pesticide components eluted from theanalysis column are first subjected online to thermalhydrolysis using an alkaline solution, followed by reactionwith OPA to convert them to strongly fluorescingsubstances. Figs. 1.3.1 and 1.3.2 show analysis results on amixed standard solution of carbofuran, methomyl, andcarbaryl using LC-VP Carbamate Analysis System. Fig.1.3.1 shows the results of the analysis of the 500 µLinjected volume of a standard solution with 5 µ g/L-concentration of each component and Fig. 1.3.2 shows theresults on a 0.1 µg/L-concentration standard solution. Fig.1.3.3 shows the results of the analysis of the 500 µLinjected volume of tap water containing 1 µ g/L


5

Column

Mobile Phase

Flow RateTemperature

Reaction Reagent 1 Flow RateTemperatureReaction Reagent 2Flow RateTemperatureDetection

: Shim-pack FC-ODS(75 mmL. × 4.6 mm I.D.)

: A: WaterB: 2-PropanolA → B: Gradient Elution

: 1.0 mL/min: 50˚C

: 0.05 M NaOH: 0.5 mL/min: 100˚C (CRB-6A): OPA Solution: 0.5 mL/min: 50˚C: Fluorescence Detector

Ex: 339 nm Em: 455 nm

min0 5 10 15 20 25 30 35

■ Peaks1.Methomyl2.Carbofuran3.Carbaryl 1

32

Fig. 1.3.1 Analysis of standards (5 µg/L, 500 µL)

■ Peaks1.Methomyl2.Carbofuran3.Carbaryl

min0 5 10 15 20 25 30 35

1 23

Fig. 1.3.2 Analysis of standards (0.1 µg/L, 500 µL)

min0 5 10 15 20 25 30 35

■ Peaks1. Methomyl2. Propoxur

3.Carbofuran 4.Bendiocarb 5.Carbaryl

1

23

45

Fig. 1.3.3 Analysis of tap water (500 µL of tap water spiked with 1 µg/L of each standard)

concentration of each standard. It is apparent that successfulseparation was achieved for bendiocarb and propoxur,which have elution peaks near carbofuran.

(Gradient Program)

Initial B.Conc. 2%

Time Func Value

6.00 B.Conc. 2

20.00 B.Conc. 15

32.00 B.Conc. 15

32.01 B.Conc. 2

44.00 STOP

1.4 Analysis of Diquat - LC

■ ExplanationThe Ministerial Ordinance related to new drinking waterquality control standards was officially announced on 30May 2003 (Japanese Ministry of Health, Labour andWelfare Ordinance 101, implemented 1 April 2004).Subsequently, 27 additional water control target items weredefined to supplement the water quality control standards(Ministry of Health, Labour and Welfare; Health PolicyBureau Ordinance No. 1010004, 10 Oct. 2003) and testmethods notified for them (Ministry of Health, Labour andWelfare; Health Service Bureau Water Supply Div.Ordinance No. 1010001, 10 Oct. 2003). *(1) Water-qualitytarget values are set for 101 pesticides, 11 of which areanalyzed by high-performance liquid chromatography(HPLC). Additional Method 11 defines the test method forone of these pesticides, diquat. This section describesexamples of the analysis of diquat conducted according toAdditional Method 11. Fig. 1.4.1 shows the structure of diquat dibromide. Thediquat target value is 0.005 mg/L. Additional Method 11designates 100x concentration by solid-phase extraction asa pre-treatment operation. *(1) Partial amendment on March 30,2006 (Japan’s Ministry of Health,

Labour and Welfare Ordinance No.0330001)

*(2) In this section, "diquat" indicates diquat dibromide (MW: 344).

6

Fig. 1.4.2 Chromatogram of diquat dibromide

0

0

2

4

6

8

10

mA

U

1

1 2 3 4 5min

■ Peak1 Diquat (0.4 mg/L)

2Br-N+N+

0

mA

U

0.1

0.2

0.3

0.0

-0.1

1 2 3

1

■ Peak1 Diquat (0.005 mg/L)

4 5min

Fig. 1.4.3 Chromatogram of diquat dibromide at high sensitivity

Fig. 1.4.1 Structure of diquat dibromide

■ Analytical ConditionsColumnMobile Phase

Flow RateTemperatureDetectionInjection Volume

: Shim-pack VP-ODS (150 mmL. × 4.6 mm I.D.): Aqueous Solution of 13.5 mL Phosphoric

Acid, 10 mL Diethylamine, and 3.0 g Sodium1-Pentanesulfonate, diluted to 1,000 mL

: 1.0 mL/min: 40˚C: UV Absorbance Detector 313 nm: 50 µL

1.5 Analysis of Iprodione, Asulam, Thiophanate-methyl, and Siduron - LC

■ ExplanationJapan's water-quality control standards cover 101 pesticidecomponents, 11 of which are analyzed by high-performanceliquid chromatography (HPLC). Additional Method 9defines the test method for four of these pesticidecomponents: iprodione, asulam, thiophanate-methyl, andsiduron. This section introduces the simultaneous analysisof iprodione, asulam, thiophanate-methyl, and siduronaccording to Additional Method 9. The target values foriprodione, thiophanate-methyl, and siduron are 0.3 mg/Land the target value for asulam is 0.2 mg/L. Fig. 1.5.2shows the chromatogram for the mixed standard solution.The concentrations are equivalent to 1/100 the targetconcentrations after conducting the pretreatment (500 xconcentration by solid-phase extraction) prescribed inAdditional Method 9. The measurement of asulam isprescribed at 270 nm and measurement of the other threecomponents is prescribed at 230 nm. These tests wereconducted using the two-wavelength simultaneousmeasurement function of the absorbance detector. Thisanalysis detected two peaks for siduron.

7

■ Peaks1 Asulam2 Thiophanate-methyl3 Siduron 14 Siduron 25 Iprodione

(0.08 mg/L)(0.08 mg/L)(0.08 mg/L)(0.08 mg/L)(0.08 mg/L)

0 2 4 6 8min

1

2

10

0

2

4

6

mA

U

mA

U

0 2

2

3

4

5

1

4 6 8 10min

0

0.1

0.2

0.3

0.4

0.5

(0.08 mg/L)(0.08 mg/L)

■ Peaks

1 Asulam2 Thiophanate-methyl

UV 270 nm UV 230 nm

Fig. 1.5.3 Chromatograms of a standard mixture of the four pesticides at high sensitivity





UV 270 nm UV 230 nm

0

0

2

4

6

8

mA

U

mA

U

2

1

2

3 4 5

4 6 8 10min

0 2 4 6 8 10min

1

2

3

4

5

0

2

4

6

8

10

Fig. 1.5.2 Chromatograms of a standard mixture of the four pesticides

Fig. 1.5.1 Structure of iprodione, asulam, thiophanate-methyl, and siduron



: Shim-pack VP-ODS (150 mmL. × 4.6 mm I.D.): 50 mM KH2PO4 (pH = 3.0)

/Acetonitrile = 45/55 (v/v) : 1.0 mL/min: 40˚C: UV Absorbance Detector 230 nm 270 nm

Asulam Siduron

Thiophanate-methyl

Iprodione

H2N

NH

HN

HN

OCH3

OO O

OCH3

NH

OCH3

OS

S

O

Cl

Cl

O

O

NHCH(CH3)2

O

OCH3

S

NH

NH

N N C

NH

1.6 Analysis of Iminoctadine Triacetate - LC

■ ExplanationHigh-performance liquid chromatography (HPLC) is usedto analyze 11 of the pesticide components covered byJapan's water-quality control standards. Additional Methods16 and 17 define the test method for iminoctadine triacetateby the post-column method. This section introduces anexample of water analysis based on Additional Method 17.Fig. 1.6.1 shows the flow diagram for the post-columnsystem. The target value for iminoctadine triacetate is 0.006mg/L. However, Additional Method 17 prescribes 200 xconcentration after pretreatment. Fig. 1.6.2 shows theanalysis results on a 20 µ L injection of 0.01 mg/Liminoctadine triacetate standard solution. Thisconcentration is equivalent to 0.00005 mg/L in the watersample. These results indicate that this system achieveshighly sensitive measurements of iminoctadine triacetate.

8

1

■ Peak1.Iminoctadine Triacetate

0.0004

0.0003

0.0002

0.0001

0.0000

-0.0001

0 5 10min

15

Fig. 1.6.3 Chromatograms of pure water

1


0.0004

0.0003

0.0002

0.0001

0.0000

-0.0001

0 5 10min

15

Fig. 1.6.4 Chromatograms of tap water

1. Mobile Phase

2. Pump for Mobile Phase

3. Injector

4. Column Oven

5. Column

6. Reaction Reagents

7. Pumps for Reaction Reagents

8. Reaction Bath

9. Reaction Coil

10. Cooling Coil

11. Fluorescence Detector

12. Waste

911

8

7

7

6

6

5

12

41 2

3 10

Fig. 1.6.1 Flow diagram


1

0.0004

0.0003

0.0002

0.0001

0.0000

-0.0001

0 5 10min

15

Fig. 1.6.2 Chromatogram of iminoctadine triacetate (0.01 mg/L)

Upper: Pure water, spiked with 0.00005 mg/L standard substance

Lower: Pure water

■ Analytical Conditions(Separation)ColumnMobile Phase

Flow RateTemperature(Detection)Reaction Reagent 1Flow RateReaction Reagent 2Flow RateTemperatureDetectionInjection Volume

: Shim-pack VP-ODS (150 mmL. × 4.6 mm I.D.): A/B = 17/5 (v/v)

A: Aqueous Solution of 14.1 g Sodium Perchlorate, 1.8 mL Lactic Acid, and 400 mgSodium Hydroxide, diluted to 1,000 mL

B: Acetonitrile: 0.6 mL/min: 50˚C

: 0.5 M NaOH: 0.2 mL/min: 3 g/L Ninhydryn Solution: 0.1 mL/min: 90˚C: Fluorescence Detector Ex:395 nm Em:500 nm: 20 µL

Upper: Tap water, spiked with 0.00005 mg/L standard substance

Lower: Tap water

9

1.7 Analysis of Glyphosate - LC

■ ExplanationHigh-performance liquid chromatography (HPLC) is usedto analyze 11 of the pesticide components covered byJapan's water-quality control standards. Additional Methods12 and 15 define the test method for glyphosate. AdditionalMethod 12 defines an analytical method using pre-columnderivatization with 9-fluorenylmethyl chloroformate(FMOC-Cl) and Additional Method 15 defines an analyticalmethod using post-column derivatization with o-phthalaldehyde. This section introduces an example ofglyphosate analysis based on Additional Method 12. Thetarget value for glyphosate is 2 mg/L. However, the methodprescribes the simultaneous measurement and addition ofthe glyphosate metabolite aminomethyl phosphonic acid(AMPA). The FMOC reagent fluoresces strongly whenreacted with a primary or secondary amine. Consequently,reacting the glyphosate and AMPA with the FMOC reagentpermits high-sensitivity detection. Fig. 1.7.1 shows thisreaction. Fig. 1.7.2 shows the analysis results on a 20 µLinjection of 0.01 mg/L glyphosate and AMPA standardsolutions (1/200 the target value). Fig. 1.7.3 shows theanalysis results on a 20 µ L injection of 0.002 mg/Lglyphosate and AMPA standard solutions. Analysis withsatisfactory S/N ratio can be achieved at low concentrationsequivalent to 1/1000 the target value.

Fig. 1.7.2 Chromatogram of a standard mixture of glyphosate and AMPA (0.01 mg/L each, 20 µL injection)



: Shim-pack VP-ODS (150 mmL. × 4.6 mm I.D.): 50 mM KH2PO4 (adjusted to pH = 2.5 with

H3PO4)/Acetonitrile = 70/30 (v/v): 0.7 mL/min: 50˚C: Fluorescence Detector Ex: 270 nm Em: 315 nm

2 4 6 8 10 12 14

50

100

150

200

250

1

2

■ Peaks1 Glyphosate2 AMPA

min

mV

C O CH

OH

Cl

Glyphosate

9-Fluorenylmethyl Chloroformate

(FMOC-Cl)

FMOC-Glyphosate

AMPA

FMOC-AMPA

HOOC CH2 NH CH2 P

OH

O

OH H2N CH2 P

OH

O

OH

2 4 6 8 10

0

10

20

30■ Peaks

1 Glyphosate2 AMPA

1

2

min

mV

Fig. 1.7.3 Chromatogram of a standard mixture of glyphosate and AMPA at high sensitivity (0.002 mg/L each, 20 µL injection)

Fig. 1.7.1 Pre-column derivatization of glyphosate and AMPA with FMOC-Cl

10

1.8 Analysis of Controlled Pesticides in Tap Water using Online Solid-Phase Extraction LC/MS - LC/MS

■ ExplanationWater-quality target values were set for 101 pesticides inrevisions to Japan's water quality standards conducted bythe Japanese Ministry of Health, Labour and Welfare in2003. The analysis of trace amounts of pesticides requiresconcentration using solid-phase extraction. However,concentration by solid-phase extraction is a difficult task as:1) it requires processing of 500 mL water sample;2) differences in injection rates into the solid-phase column

affect the recovery rate;3) solvent elimination must be conducted by nitrogen

purging or some other method;4) concentration takes a lot of time and effort.The Online Solid-Phase Extraction LC/MS Systemautomates the pretreatment and is linked online to theLC/MS instrument. The operator can analyze pesticides inwater simply by loading a sample in the system. Thissection introduces the simultaneous analysis of 15 pesticidecomponents using a C18 cartridge. Fig. 1.8.1 shows theanalysis results using this system (selected ion monitoring)for 1 mL water sample made by spiking purified water to0.5 µg/L with each of the pesticides.

■ Analytical ConditionsColumnMobile Phase AMobile Phase BGradient Program

Flow RateCartridge

Injection VolumeColumn TemperatureProbe Voltage

CDL TemperatureBlock-Heater TemperatureNebulizer Gas Flow RateDrying Gas PressureCDL VoltageQ-array DC VoltageQ-array RF

: L-column ODS (150 mmL. × 2.1 mm I.D.): 0.1 % Formic Acid-Water: Acetonitrile: 0 % B-95 % B (20-30 min.)0 % B (30.01-40 min.)

: 0.2 mL/min: Inertsil ODS-3, 7 µm

(10 mmL. × 2.0 mm I.D.): 1 mL (PROSPEKT-2): 40˚C : +4.5 kV (ESI-Positive Mode): –3.5 kV (ESI-Negative Mode): 200˚C: 150˚C: 1.5 L/min.: 0.2 MPa: C-Mode: S-Mode: 150

1. Thiram 2. Simazine 3. Thiobencarb18. Carbofuran66. Dimethoate68. Diuron

MW 240MW 201MW 257MW 221MW 229MW 232

84. Daimuron86. Bensulfuron-methyl90. Azoxystrobin94. Harosulfuron-methy95. Flazasulfuron98. Siduron

MW 268MW 410MW 403MW 434MW 407MW 232

17. Bentazone19. 2,4-Dichlorophenoxy

acetic acid (2,4-D)20. Triclopyr

MW 240MW 220

MW 255

ESI-Positive ESI-Negative

5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0

0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

2.50

2.75

3.00

3.25

3.50

3.75

(x 100,000)

2:253.90 (3.00)2:218.90 (3.00)2:239.00 (1.00)1:258.00 (1.00)1:269.10 (1.00)1:435.10 (1.00)1:404.10 (1.00)1:233.10 (1.00)1:408.10 (1.00)1:411.10 (1.00)1:240.90 (1.00)1:222.10 (1.00)1:202.00 (1.00)1:229.90 (1.00)

66 18

98

86

1

68 95

9084

394

17

19

20

2

Fig. 1.8.1 SIM chromatograms on 1 mL 0.5 µg/L spiked sample using solid-phase extraction

11

1.9 Simultaneous Analysis of Pesticides Covered by the Water Quality Control Standards using LC/MS (1) - LC/MS

■ ExplanationCurrently, Japan's water-quality control standards cover101 pesticide components under Item 15, Pesticides. As theanalysis results are expressed using the Total PesticideMethod, in principle each pesticide must be measured downto 1/100 the concentration target value. This sectionintroduces an example of a simultaneous LC/MS analysisusing a divinyl benzene-N-vinyl pyrrolidone copolymersolid-phase column and an activated carbon solid-phasecolumn linked to perform pretreatment concentration (Fig.1.9.1) of the 29 pesticide compounds. The analysis sampleswere made from ion-exchange water and river water spikedwith each of the pesticides to a concentration 1/100 of thetarget value.


Flow RateInjection VolumeColumn TemperatureProbe Voltage

CDL TemperatureBlock-Heater TemperatureNebulizer Gas Flow RateDrying Gas PressureCDL VoltageQ-array DC Voltage

: L-column ODS (150 mmL. × 2.1 mm I.D.): 0.1 % Formic Acid-Water: Acetonitrile: 0 % B-95 % B (40 min)0 % B (40.01 min) -stop (50 min)

: 0.2 mL/min: 10 µL: 40˚C : +4.5 kV (ESI-Positive Mode): –3.5 kV (ESI-Negative Mode): 250˚C: 200˚C: 1.5 L/min.: 0.2 MPa: Default Value: Default Value

1

18

21

26

28

36

42

48

55

58

68

74

75

76

82

86

87

90

95

96

98

98

17

19

20

45

84

94

Thiram

Carbofuran

Acephate

Iprodione

Oxine-Cu

Asulam

Bensulide

Carbaryl

Thiophanate-methyl

Carpropamid

Diuron

Methomyl

Benomyl

Benfuracarb

Probenazole

Bensulfuron-methyl

Tricyclazole

Azoxystrobin

Flazasulfuron

Thiodicarb

Siduron-A

Siduron-B

Methyl 2-benzimidazolylcarbamate

(MBC) (decomposition

product of Benomyl)

Bentazon

2,4-D

Triclopyr

Mecoprop

Daimuron

Harosulfuron-methyl

241

222

184

330

146

231

356

202

343

334

233

163

291

411

224

411

190

404

408

355

233

233

192

239

219

196

213

313

433

0.02

0.005

0.08

0.3

0.04

0.2

0.1

0.05

0.3

0.04

0.02

0.03

0.02

0.04

0.05

0.4

0.08

0.5

0.03

0.08

0.3

0.3

0.2

0.03

0.006

0.005

0.8

0.3

Mode No. Pesticide name Monitor ion (m/z)

Target value (mg/L)

–– ––

Positive

Negative

Table 1.9.1 List of pesticides

Activated carbon solid-phase column

500 mL water sample

Deliver at 10 - 20 mL/min.

Backflush elution

Add water to 1 mL

Analyze 10 µLLC/MS

Solid-phase extraction

Drying

Elution

Concentration, constant volume

0.5 g/L EDTA-2Na adjusted to pH 3.5 with nitric acid (1 + 10) Spiked with pesticide standard samples

Fig. 1.9.1 Solid-phase extraction flow

12

Fig. 1.9.2 SIM chromatograms of pesticides at 1/100 concentration (ESI-positive)(pesticides with target value ≥ 0.08 mg/L)(top: spiked ion-exchange water sample; bottom: spiked river water sample)

2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min0.00

0.25

0.50

0.75

1.00

1.25

(´1,000,000)

356.00 (5.00)330.05 (10.00)404.15 (0.10)411.15 (0.50)233.00 (0.50)355.00 (1.00)343.05 (1.00)190.00 (1.00)231.00 (1.00)192.00 (1.00)184.00 (5.00)

36_Asulam

36_Asulam

21_Acephate

21_Acephate

Carbendazim (MBC)

Carbendazim (MBC)

Spiked ion-exchange water sample

87_Tricyclazole

87_Tricyclazole

55_Thiophanate-methyl

55_Thiophanate-methyl

98_Siduron

98_Siduron

42_Bensulide

42_Bensulide

96_Thiodicarb

96_Thiodicarb

86_Bensulfuron-methyl

86_Bensulfuron-methyl

90_Azoxystrobin

90_Azoxystrobin

26_Iprodione

26_Iprodione

2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min0.00

0.25

0.50

0.75

1.00

1.25

(´1,000,000)

356.00 (5.00)330.05 (10.00)404.15 (0.10)411.15 (0.50)233.00 (0.50)355.00 (1.00)343.05 (1.00)190.00 (1.00)231.00 (1.00)192.00 (1.00)184.00 (5.00) Spiked river water sample

2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75(´100,000)

334.05 (1.00)291.00 (1.00)408.10 (1.00)411.15 (0.50)233.00 (0.50)223.90 (2.00)202.05 (1.00)241.00 (2.00)222.00 (1.00)163.00 (1.00)146.00 (0.50)

28_Oxine-Cu

28_Oxine-Cu

95_Flazasulfuron

95_Flazasulfuron

82_Probenazole

82_Probenazole

68_Diuron

68_Diuron

1_Thiram

1_Thiram

48_Carbaryl

48_Carbaryl

18_Carbofuran

18_Carbofuran

74_Methomyl

74_Methomyl

58_Carpropamid

58_Carpropamid


2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75(´100,000)

334.05 (1.00)291.00 (1.00)408.10 (1.00)411.15 (0.50)233.00 (0.50)223.90 (2.00)202.05 (1.00)241.00 (2.00)222.00 (1.00)163.00 (1.00)146.00 (0.50) Spiked river water sample

Fig. 1.9.3 SIM chromatograms of pesticides at 1/100 concentration (ESI-positive)(pesticides with target value < 0.08 mg/L)(top: spiked ion-exchange water sample; bottom: spiked river water sample)


13

Fig. 1.9.4 SIM chromatograms of pesticides at 1/100 concentration (ESI-negative)(pesticides with target value ≥ 0.1 mg/L)(top: spiked ion-exchange water sample; bottom: spiked river water sample)

Fig. 1.9.5 SIM chromatograms of pesticides at 1/100 concentration (ESI-negative)(pesticides with target value < 0.1 mg/L)(top: spiked ion-exchange water sample; bottom: spiked river water sample)



2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25(´ 100,000)

313.10 (1.00)433.00 (1.00)239.00 (1.00)

17_Bentazon

17_Bentazon

94_Harosulfuron-methyl

94_Harosulfuron-methyl

84_Daimuron

84_Daimuron

Spiked river water sample

2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25(´ 100,000)

313.10 (1.00)433.00 (1.00)239.00 (1.00)


2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min2.0

3.0

4.0

5.0

6.0

7.0

8.0(´ 1,000)

212.95 (1.00)195.85 (1.20)218.90 (1.00)140.85 (1.00)

19_2,4-D

19_2,4-D

20_Triclopyr

20_Triclopyr

45_Mecoprop

45_Mecoprop

Spiked river water sample

2.5 5.0 7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0 27.5 30.0 32.5 35.0 37.5 min2.0

3.0

4.0

5.0

6.0

7.0

8.0(´ 1,000)

212.95 (1.00)195.85 (1.20)218.90 (1.00)140.85 (1.00)

14

1.10 Simultaneous Analysis of Pesticides Covered by the Water QualityControl Standards using GC/MS (1) - GC/MS

■ ExplanationThe 2003 partial revisions to the Japanese Waterworks Lawlumped all pesticides into one item in the water-qualitycontrol standards and adopted the Total Pesticide Methodas the new detection criteria. With the Total PesticideMethod, the total of each detected value divided by thetarget value defined for each component must not exceed 1. Water-quality target values are set for 101 pesticides, ofwhich 73 are analyzed by GC/MS. These include onepesticide measured as VOC, 1,3-dichloropropene, and fourpesticides requiring derivatization: bentazone, 2,4-D,triclopyr, and mecoprop. This section introduces an example of the simultaneousanalysis of 74 components: 71 pesticides (excluding 1,3-dichloropropene that is measured as VOC and trichlorfon)and three internal standards (Phenanthrene-d, Anthracene-d,and 9-bromoanthracene).

■ Analytical ConditionsInstrument-GC-ColumnColumn Temperature

Carrier GasHigh-Pressure InjectionInjection Inlet TemperatureInjection MethodInjection Volume -MS-Interface TemperatureIon-Source TemperatureIonizationScan RangeScan Interval

: GCMS-QP2010

: Rtx-5MS (30 m × 0.25 mm I.D. df=0.25 µm): 80˚C (2 min) -20˚C/min-180˚C

-5˚C/min-280˚C (10 min): He, 45.0 cm/s, Constant Linear Velocity Mode: 250 kPa (2 min.): 260˚C: Splitless (2 min.): 2 µL

: 260˚C: 230˚C: EI: m/z 40-550: 0.5 s

Peak number

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

24

25

26

Pesticide name

Dichlorvos

Dichlobenil

Etridiazole

Chloroneb

Isoprocarb

Molinate

Mecoprop

Fenobucarb

2,4-D

Trifluralin

Benfluralin

Pencycuron

Triclopyr

Dimethoate

Simazine (CAT)

Atrazine

Propyzamide

Pyroquilone

Phenanthrene-d

Diazinon

Anthracene-d

Ethylthiometon

Chlorothalonil

Iprobenfos

Bromobutide

Terbucarb

Target value (mg/L)*

0.008

0.01

0.004

0.05

0.01

0.005

0.005

0.03

0.03

0.06

0.08

0.04

0.006

0.05

0.003

0.01

0.05

0.04

IS

0.005

IS

0.004

0.05

0.008

0.04

0.02

Peak number

53

54

55

56

57

58

59

60

61

62

63

64

65

66

67

68

69

70

71

72

73

74

75

76

-

Pesticide name

Flutolanil

Isoprothiolane

Pretilachlor

CNP-amino

Buprofezin

Isoxathion

-Endosulfan

Mepronil

Chlornitrofen

Edifenphos

Propiconazole 1

Propiconazole 2

Thenylchlor

Pyributicarb

Iprodione

Pyridafenthion

EPN

Piperophos

Bifenox

Anilofos

Pyriproxyfen

Mefenacet

Cafenstrole

Etofenprox

Trichlorfon


0.2

0.04

0.04

0.02

0.008

0.01

0.1

0.0001

0.006

0.05

0.2

0.02

0.3

0.002

0.006

0.0009

0.2

0.003

0.2

0.009

0.008

0.08

0.03

Peak number

27

28

29

30

31

32

33

34

35

36

37

38

39

40

41

42

43

44

45

46

47

48

49

50

51

52

Pesticide name

Bentazone

Simetryn

Tolclofos-methyl

Alachlor

Metalaxyl

Dithiopyr

Fenitrothion

Esprocarb

Malathion.

Thiobencarb

Fenthion

Chlorpyrifos

Fthalide

Dimethametryn

Pendimethalin

Methyldymron

Isofenphos

Captan

Dimepiperate

Phenthoate

Procymid

Methidathion

9-Bromoanthracene

-Endosulfan

Butamifos

Napropamide


0.2

0.03

0.2

0.01

0.05

0.008

0.003

0.01

0.05

0.02

0.001

0.03

0.1

0.02

0.1

0.03

0.001

0.3

0.003

0.004

0.09

0.004

IS

0.01

0.01

0.03

Table 1.10.1 List of pesticides and target values (mg/L)

* Target values quoted from the Japanese Ministry of Health, Labour and Welfare home page - http: //www.mhlw.go.jp/shingi/2003/04/s0428-4e.html

15

7.5 10.0 12.5 15.0 17.5 20.0 22.5 25.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0(x1,000,000)

TIC – Overall

TIC – Enlargement 5.5 to 11.8 minutes



6.0 7.0 8.0 9.0 10.0 11.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0(x1,000,000)

12

3

4 5 6 78

9 10111213

14 15 1617

18 19

20

21

22 2324

12.0 12.5 13.0 13.5 14.0 14.5 15.0 15.5 16.0

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00(x1,000,000)

25 26

27

28

29

30 3132

33

34

35

36

37

38

3940

4142

43

4445

46

4748

49

50 5152

53 54 55

17.0 18.0 19.0 20.0 21.0 22.0 23.0 24.0 25.0 26.0 27.0

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00(x1,000,000)

5657

5859

60

61

6263

6465 66

67

68

69

70 71

7273

74 75 76

Fig. 1.10.1 Scan TIC of standard mixture of pesticides (0.1 mg/L each component)

1.10 Simultaneous Analysis of Pesticides Covered by the Water QualityControl Standards using GC/MS (2) - GC/MS

16

1.11 Analysis of Bromate by Post-Column Ion Chromatography (1) - LC

■ ExplanationBromate ions are classed as disinfection byproducts createdby ozonation or treatment with sodium hypochlorite.A standard value was set for bromate ions in tap water inthe Ministerial Ordinance related to new drinking waterquality control standards that was officially announced on30 May 2003 (Japanese Ministry of Health, Labour andWelfare Ordinance 101, implemented 1 April 2004). Thestandard value was set at 0.010 mg/L. The test method forbromates was notified in the Ministry of Health, Labourand Welfare Notification No. 261, dated 22 July 2003. Thenotified method employs post-column ion chromatographywith detection using the tribromide ion method. This post-column method involves a 2-stage reaction: the firstreaction stage converts the bromate to tribromide ions usingpotassium bromate/nitric acid solution (Fig. 1.11.1), and thesecond reaction stage uses a sodium nitrite solution toensure linearity of the calibration curve in the low-concentration region. An analysis accuracy of CV10 % isdemanded at 0.001 mg/L (1 µ g/L), which is 1/10 thestandard concentration value.

■ Analytical Conditions(Separation)ColumnMobile PhaseFlow RateTemperature

Reaction 1Reaction Reagent Flow RateReaction TemperatureReaction 2Reaction Reagent Flow RateReaction TemperatureDetection

: Shim-pack IC-SA2 (250 mmL. × 4.0 mm I.D.): 12 mM NaHCO3 + 0.6 mM Na2CO3

: 1.0 mL/min.: 40˚C

: 1.5 M KBr + 1.0 M H2SO4

: 0.4 mL/min: 40˚C

: 12 mM NaNO2

: 0.2 mL/min: 40˚C: UV Absorbance Detector 268 nm

Water Quality Item : Bromate Ions

Water Quality Standard : 0.010 mg/L

Derivatization : Tribromide Ion Method

Detection : UV Absorbance Detector 268 nm

(Post-Column Reactions)

min1 2 3 4 5 6 70

BrO3–

mA

U

0.0

0.4

0.8

1.2

1.6

Fig. 1.11.2 Chromatogram of tap water

min1 2 3 4 5 6 70

mA

U

0.0

0.4

0.8

1.2

1.6

BrO3–

Fig. 1.11.3 Chromatogram of tap water spiked with 1 µg/L bromate

BrO3-+5Br-+6H+ 3Br2+3H2O

Br2+Br- Br3-

Fig. 1.11.1 Reaction formula

17

1.11 Analysis of Bromate by Post-Column Ion Chromatography (2) - LC

min0 1 2 3 4 5 6 7

mA

U

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5 BrO3–

10 µg/L

5 µg/L

1 µg/L

Fig. 1.11.6 Chromatograms of bromate standard

min 0 1 2 3 4 5 6 7

mA

U

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

Retention TimeBrO3

Repeatability (CV%)

(n=10, 100 µL Inj.)

0.102.10Peak Area

BrO3–

Fig. 1.11.7 Repeatability of bromate standard (1 µg/L)

12, 3

456

Pump for Mobile PhasePumps for Reaction ReagentsDegasserAutosamplerColumn

7, 89

1011

12,13

Reaction CoilsColumn OvenUV DetectorMobile PhaseReaction Reagents

9 108765

11

12

13 4

1

2

3

Fig. 1.11.4 Flow diagram

00

50000

100000

150000

200000

250000

300000

350000

400000

20 40 60 80 100 120

r2=0.9999

Fig. 1.11.5 Calibration curve (0.5-100 µg/L)

18

1.12 Speciation Analysis of Cyanogen Compounds by Post-Column Ion Chromatography (1) - LC

■ ExplanationIn Japan, a standard value was set for cyanide ions andcyanogen chloride in tap water in the Ministerial Ordinancerelated to new drinking water quality control standards thatwas officially announced on 30 May 2003 (Ministry ofHealth, Labour and Welfare Ordinance 101, implemented 1April 2004). The standard value was set at 0.010 mg/L. The test method for cyanide ions and cyanogen chloridewas notified in the Ministry of Health, Labour and WelfareNotification No. 261, dated 22 July 2003, and partiallyrevised on 1 April, 2005. The notified method employs ananalytical method using post-column ion chromatographyto separate and quantitate the cyanide ions and cyanogenchloride by species. Detection involves derivatization usingthe 4-pyridinecarboxylic acid/pyrazolone method, followedby separation of the cyanide ions and cyanogen chloride inthe analysis column and then conducting speciation analysisusing two types of reaction liquid. Instruments for thisanalysis must provide an analysis accuracy of CV10% at0.001 mg/L (1 µ g/L), which is 1/10 the standardconcentration value.

■ Analytical Conditions(Separation)Column

Mobile Phase


Reaction 1Reaction Reagent

Flow RateReaction TemperatureReaction 2Reaction Reagent

Flow RateReaction TemperatureDetection

: Shim-pack Amino-Na (100 mmL. × 6.0 mm I.D.)

: 10 mM Sodium Tartrate Buffer Solution(pH 4.2)

: 0.6 mL/min: 40˚C

: 100 mM Phosphate Buffer Solutionincluding 1.8 mM Chloramine T

: 0.5 mL/min: 40˚C

: 14.4 mM 1-Phenyl-3-Methyl-5-Pyrazolone +48.3 mM Sodium 4-Pyridinecarboxylate

: 0.5 mL/min: 100˚C: UV-VIS Absorbance Detector 638 nm

Water Quality Item : Cyanide Ions and Cyanogen Chloride

Water Quality Standard : 0.010 mg/L

Derivatization : 4-Pyridinecarboxylic Acid / Pyrazolone

Detection : UV-VIS Absorbance Detector 638 nm

(Post-Column Reactions)

Fig. 1.12.1 Chromatogram of tap water Fig. 1.12.2 Chromatogram of tap water spiked with 1 µg/L cyanide ions

min0 2 4 6 8 10

mA

U

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

CNCl

mA

U

-0.2

0.0

0.2

0.4

0.6

0.8

1.0

min0 2 4 6 8 10

19

Fig. 1.12.5 Calibration curve for cyanide ions (0.5-100 µg/L) Fig. 1.12.6 Calibration curve for cyanogen chloride (0.5-100 µg/L)

Fig. 1.12.3 Flow diagram Fig. 1.12.4 Repeatability of cyanide ions and cyanogen chloride standards (1 µg/L each)

0

100000

200000

300000

400000

500000

600000

700000

800000

900000

1000000

0 20 40 60 80 100

CN : r2=0.9999

12, 3

456

7, 8

Pump for Mobile PhasePumps for Reaction ReagentsDegasserAutosamplerColumnReaction Coils

9101112

13, 14

Column OvenReaction OvenUV-VIS DetectorMobile PhaseReaction Reagents

9 11

8

765

12

13

14 4

1

2

3

10

0

100000

200000

300000

400000

500000

600000

700000

800000

900000

1000000

0 20 40 60 80 100

CNCl : r2=0.9998

min

0 1 2 3 4 5 6 7 8 9 10

mA

U

0.0

0.5

1.0

1.5

2.0

CN–

CNCl

Retention TimeCN

Repeatability (CV%)

(n=10, 100 µL Inj.)

CNCl0.05 0.020.69 1.72Peak Area

1.12 Speciation Analysis of Cyanogen Compounds by Post-Column Ion Chromatography (2) - LC

20

1.13 Analysis of Nitrite Nitrogen - Ion Chromatograph

■ ExplanationNitrite-nitrogen is one of the water control target items thatshould be focused on in a stagnant water source, such as alake or marsh. Ion chromatography is used as the inspectionmethod for nitrite-nitrogen. The standard value for nitrite-nitrogen is provisionally set at 0.05 mg/L max. It is difficultto achieve high sensitivity for the analysis of nitrite by ionchromatography due to the effects of the large number ofchloride ions. Using an additional UV absorbance detectorcan enhance the measurement sensitivity for nitrite ions byreducing the effects of the chloride ions. This occursbecause nitrite ions (and bromide ions and nitrate ions)exhibit absorbance in the UV range (around 210 nm),whereas chloride ions do not.

■ Analytical ConditionsInstrument


Injection VolumeSample(Fig. 1.13.1 and 1.13.2)


: Shim-pack IC-SA2 (250 mmL. × 4.0 mm I.D.): 12 mM NaHCO3 + 0.6 mM Na2CO3

: 1.0 mL/min: 30˚C: Electroconductivity DetectorUV Absorbance Detector 210 nm

: 50 µL: F ; 0.5 mg/L, Cl ; 1 mg/L

NO2-N ; 0.5 mg/L, Br ; 1 mg/L

NO3-N ; 0.75 mg/L, PO4 ; 3 mg/L

SO4 ; 4 mg/L

0

0

1.0

2.0

3.0

4.0

µS/c

m

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15min

F-

Cl-

NO2-

NO3-

SO42-

F-

Cl-

NO2-

Br-

NO3-

PO43-

SO42-

0

0

1.0

2.0

µS/c

m

3.0

4.0

5.0

2 4 6 8min

10 12 14 16 18

0

0

10

20

mA

U

30

40

50

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15min

NO2-

NO3-

Br-

0

0

50

mA

U

100

2 4 6 8min

10 12 14 16 18

NO2-

Br-

NO3-

Fig. 1.13.3 Chromatogram for tap water spiked with 0.05 mg/L nitrite-nitrogen (Electroconductivity detector)

Fig. 1.13.1 Chromatogram for standard mixture of 7 components (Electroconductivity detector)

Fig. 1.13.4 Chromatogram for tap water spiked with 0.05 mg/L nitrite-nitrogen (UV detector)

Fig. 1.13.2 Chromatogram for standard mixture of 7 components (UV detector)

21

1.14 Analysis of Chlorite, Chlorate, and Chlorine Dioxide - Ion Chromatograph

■ ExplanationChlorite, chlorate, and chlorine dioxide require particularattention from the viewpoint of the equipment andchemicals used for water treatment and from the viewpointof the disinfection byproducts. Water-treatment plants thatinject chlorine dioxide into drinking water or use it duringthe purification process are required to conform to thesewater-quality targets. Ion chromatography is used as theinspection method for these components. The standardvalue for each component set at 0.6 mg/L max. Chlorinedioxide cannot be directly measured by ion chromatography,as it does not exist as ions in water. However, reducingchlorine dioxide with an aqueous solution of sodium nitritepermits the quantitation of chlorine dioxide as chlorite ions.Fig. 1.14.1 shows the chromatogram for a standard mixtureof chlorite and chlorate ions (0.6 mg/L each). Fig. 1.14.2shows the chromatogram of 9 components, with 7 inorganicanion components in addition to the chlorite and chlorateions (1 mg/L each). Fig. 1.14.3 shows the chromatogramfor chlorite ions in tap water spiked with 0.06 mg/L


ColumnMobile Phase Flow RateTemperatureDetectionInjection Volume


: Shim-pack IC-SA3 (250 mmL. × 4.0 mm I.D.): 3.6 mM Na2CO3

: 0.8 mL/min: 45˚C: Electroconductivity Detector : 50 µL

chlorite, with phosphate buffer and sodium nitrite added.Fig. 1.14.4 shows the chromatogram for chlorite andchlorate ions in tap water spiked with 0.06 mg/L chloriteand chlorate and with phosphate buffer added. These resultsindicate that analysis is possible in the presence of highconcentrations of phosphate and nitrite ions.

0

500nS/c

m

1000

1500

-2000

-4000

ClO2-

ClO3-

0 2 4 6 8 10 12min

14 16 18 20 22 24

Fig. 1.14.1 Chromatogram for standard mixture of chlorite and chlorate

6000

4000

nS/c

m

2000

0

0 2 4 6 8 10 12min

ClO2-

ClO3-

F-

Cl-

NO2-Br- NO3-

PO43-

SO42-

14 16 18 20 22 24

Fig. 1.14.2 Chromatogram for standard mixture of 9 components

ClO2-

0 2 4 6 8 10 12min

14 16 18 20 22 24

6000

4000

nS/c

m

2000

0

ClO2-

Fig. 1.14.3 Chromatogram for tap water spiked with 0.06 mg/L chlorite

0 2 4 6 8 10 12min

14 16 18 20 22 24

ClO2-ClO3-

0

-2000

-4000

2000

4000

nS/c

m

Fig. 1.14.4 Chromatogram for tap water spiked with 0.06 mg/L chlorite and chlorate

22

1.15 Analysis of Isocyanuric Acid - LC

■ ExplanationThe 2001 revision of the Japanese Drinking Water TestMethod added isocyanuric acid as a controlled substance.Isocyanuric acid is normally used as a disinfectant inswimming pools, but is also used to sterilize drinking waterin overseas refugee camps. Fig. 1.15.1 shows the analysisresults for an isocyanuric acid standard. A 10 mg/L samplewas prepared from sodium dichloroisocyanate, and 20 µLof sample was injected. This sample must be prepared whenrequired, as isocyanuric acid is unstable in water andreadily decomposes. Fig. 1.15.2 shows the UV spectrum ofisocyanuric acid detected by a photodiode array detector.As isocyanuric acid absorbs UV in the short-wavelengthrange only, careful column selection is required to ensuresufficient retention to separate impurities in the sample.



: Shodex RSpak DE-613 (150 mmL. × 6.0 mm I.D.): 10 mM Sodium Phosphate Buffer Solution

(pH 7.0): 0.8 mL/min: 40˚C: UV Absorbance Detector 220 nm: Photodiode Array Detector 200-300 nm

■ Peak1. Isocyanuric acid

1

min0 2 4 6 8

nm200 250 300 350

mA

U

Fig. 1.15.1 Chromatogram for isocyanuric acid Fig. 1.15.2 UV spectrum of isocyanuric acid standard

23

1.16 Analysis of Anionic Surfactants - LC

■ ExplanationThe new drinking water quality control standards set a totalconcentration of 0.2 mg/L as the limit for 5 anionic surfactants.HPLC and flowpath absorption spectrophotometry areprescribed as test methods for anionic surfactants. Flowpathabsorption spectrophotometry for use up to 31 March2007.) This section introduces an example of the analysis ofthe 5 anionic surfactant components using fluorescenceHPLC. Fig. 1.16.2 shows the analysis results for a 20 µLinjection of a mixed standard solution of 5 anionicsurfactant standards (2.0 mg/L each, total 10.0 mg/L).These concentrations are equivalent to 1/5 the standardvalues after pretreatment according to the new water qualityinspection method (250 x concentration of water sample).Fig. 1.16.3 shows the analysis results on a concentrated tapwater sample. The lower chromatogram is for tap water andthe upper chromatogram is for tap water spiked withanionic surfactant standards.


Fig. 1.16.2 Chromatogram of anionic surfactants(2 mg/L each, total 10 mg/L, 20 µL injected volume)

Fig. 1.16.3 Chromatogram of tap water (20 µL injected volume)Top: Tap water spiked with 0.004 mg/L of each

components, total 0.02 mg/LBottom: Tap water

■ Peaks1.C10

2.C11

3.C12

4.C13

5.C14

1

min0 5 10 15 20 25

Vol

ts

0.00

0.02

0.04

0.06

0.08

0.10

2

34

5

Spiked tap water

Tap water

min0 5. 10 15 20 25

Vol

ts

0.00

0.02

0.04

0.06

0.08

0.101

2

3

4

5

■ Peaks1.C10

2.C11

3.C12

4.C13

5.C14

n = 10: Sodium Decylbenzenesulfonate n = 11: Sodium Undecylbenzenesulfonate n = 12: Sodium Dodecylbenzenesulfonate n = 13: Sodium Tridecylbenzenesulfonate n = 14: Sodium Tetradecylbenzenesulfonate

CnH2n+1

SO3Na

Fig. 1.16.1 Structure of Anionic Surfactants

Note: Analysis at 500 x concentration before partial revision in March 2005.

ColumnMobile Phase

Flow RateTemperatureDetectionInjection Volume

: Shim-pack VP-ODS (250 mmL. × 4.6 mm I.D.): Water/Acetonitrile = 35/65 (v/v)

(Including 0.1 M Sodium Perchlorate): 1.0 mL/min: 40˚C: Fluorescence Detector Ex: 221 nm Em: 284 nm: 20 µL

24

1.17 Analysis of Microcystins using Online Solid-Phase Extraction LC/MS - LC/MS

■ ExplanationMicrocystins are liver toxins and carcinogens that arecaused by the abnormal proliferation of blue-green algaedue to eutrophication of lakes and marshes. Themeasurement of these toxins is becoming increasinglyimportant in areas that take the raw water source for theirtap water supply from lakes or marshes. The 2003 revision of the Japanese Drinking Water TestMethod designated microcystin LR as a controlled item.The 2001 Drinking Water Test Method prescribed solid-phase extraction to adsorb 500 mL water sample, elution inan organic solvent and concentration of the eluate to 1 mL,and then analysis by HPLC or LC/MS. Conventionally, theextraction process required an experienced operator, as therecovery rate by solid-phase extraction differs according tothe solid-phase production lot and the water sample flowrate. The long time required for nitrogen purging and otherpretreatment operations also posed a problem for theoperators. Connecting the PROSPECT 2 automatic onlinesolid-phase extraction system to the LC/MS permits themeasurement of microcystin RR, YR, and LR down to 1/10the standard value, simply by loading the water sample intothe autosampler. As shown in Fig. 1.17.1, PROSPECT 2automates the solid-phase activation and equilibration, andsample loading. Components retained in the solid-phasecartridge are eluted online to the HPLC mobile phase,eliminating the need for nitrogen purging (evaporation) andreconstruction. Incorporating a variety of pretreatmentmethods allows automatic determination of the solid-phaseextraction conditions and the elimination of impurities byvalve switching and washing operations. Fig. 1.17.2 shows


Flow RateCartridgeInjection VolumeColumn TemperatureProbe VoltageCDL TemperatureBlock-Heater TemperatureNebulizer Gas Flow RateDrying Gas PressureCDL VoltageQ-array DC VoltageQ-array RF

: Shim-pack VP-ODS (150 mmL. × 2.0 mm I.D.): 0.1 % Formic Acid-Water: Acetonitrile: 10 % B-60 % B (15-20 min)

-100 % B (20.01-25 min)-10 % B (25.01-35 min)

: 0.2 mL/min: Inertsil ODS-3, 7 µm (10 mmL. × 2.0 mm I.D.): 5 mL (PROSPECT 2): 40˚C : +4.5 kV (ESI-Positive Mode): 200˚C: 200˚C: 1.5 L/min.: 0.1 MPa: +25 V (ESI-Positive Mode): S-Mode: 150

the SIM chromatograms from solid-phase extraction of 5mL of purified water samples spiked with 50 ng/Lmicrocystin RR, YR, and LR. Each sample is processed in35 minutes, as all the solid-phase extraction operationsfrom solid-phase activation to sample loading arecompleted during equilibration at the initial gradientconcentration.

2.5 5.0 7.5 10.0 12.5 15.0 17.5 min

2500

5000

7500

10000

12500

15000

17500

20000

22500

25000

27500

30000

Int.

498.50(2.80)523.50(3.39)520.00(1.00)

Microcystin RRm/z 520.00(M+2H)2+

Microcystin YRm/z 523.50(M+2H)2+

Microcystin LRm/z 498.50(M+2H)2+

Fig. 1.17.2 SIM chromatograms of microcystin RR, YR, and LR

Activa

tion

Equilib

ratio

n

Sample

load

ing

Was

hes

Analyt

e elut

ion

Evapo

ratio

n

Recon

stitut

ion

Injec

tion

anal

. col

umn

anal

. col

umn

PR

OS

PE

KT

OF

F-L

INE

"SWITCH VALVE"

N2

Fig. 1.17.1 Solid-phase extraction operations

25

1.18 Analysis of Chloral Hydrate and Haloacetonitriles (1) - GC/MS

■ ExplanationChloral hydrate and haloacetonitriles are byproducts of thedisinfection of tap water. The July 2001 revision of theJapanese Drinking Water Test Method adopted 1,2,3-trichloropropane as the internal standard and added twocomponents: chloroacetonitrile and bromochloroacetonitrile.Chloral hydrate and haloacetonitriles can be analyzedsimultaneously. Calibration curves were created for eachtarget component in the range from 10 µg/L to 1000 µg/Lusing the internal standard method. The solution of50 µL of 10 mg/L 1,2,3-trichloropropane was added to 2mLof each concentration sample as the internal standard tocreate the calibration curve. Figs. 1.18.1 to 1.18.7 show themass spectrum, the SIM mass chromatogram for a 10 µg/Lsample, and the calibration curve for each component.

■ Analytical ConditionsInstrument-GC-ColumnColumn TemperatureCarrier GasInjection MethodInjection Inlet Temperature Injection Volume-MS-Interface Temperature Ion-Source Temperature

: GCMS-QP2010

: DB-1 (30 m × 0.25 mm I.D. df=1.0 µm): 40˚C (10 min) -20˚C/min-200˚C (3 min): He, 43 cm/s, Constant Linear Velocity Mode: Splitless (2 min.): 250˚C: 1 µL

: 250˚C: 200˚C

m/z

100

30 40 50 60 70

40

487575 1,879

5.7

75*1.00

77*1.00

f(x)=0.002939*x-0.010103Correlation coefficient (R) =0.999985

1.0[*10^3]

0.0 0.5

2.0

[*10^0]

095.8

1.0

Fig. 1.18.2 Chloroacetonitrile

m/z

100

30 50 70 90 110 130

35

47

60

82

8585

111113

146

431

8.0 8.4

82*1.00

111*1.00

146*1.00

f(x)=0.001145*x+0.000235Correlation coefficient (R) = 0.999999

1.0[*10^3]

0.0 0.5

1.0

[*10^0]

0.0

0.5

Fig. 1.18.1 Chloral hydrate

26

1.18 Analysis of Chloral Hydrate and Haloacetonitrile (2) - GC/MS

m/z

100

30 40 50 60 70 80 90 100 110

3949

61

75

97

110

114

94,550

15.0

75*1.00

110*1.00

m/z

100

30 50 70 90 110 130 150 170 190

39 79 91

118

160

199

887

14.0 14.6

118*1.00

120*1.00


[*10^3]1.00.0 0.5

8.0[*10^-1]

490.5

4.0

m/z

100

30 50 70 90 110 130 150

39 47

74

93 118 128153

1,686

12.0 12.5

74*1.00

155*1.00


[*10^3]1.00.0 0.5

1.0

[*10^0]

105.4

0.8

m/z

100

30 40 50 60 70 80 90 100

38

47

74

86 108

1,468

7.0 7.7

74*1.00

82*1.00


1.0[*10^3]

0.0 0.5

2.0

[*10^0]

525.4

1.0

m/z

100

30 40 50 60 70 80 90 100 110

3547 73

86

108108108 1,559

6.0 6.7

108*1.00

110*1.00


1.0[*10^3]

0.0 0.5

2.0

[*10^0]

353.7

1.0

Fig. 1.18.3 Trichloroacetonitrile

Fig. 1.18.4 Dichloroacetonitrile

Fig. 1.18.5 Bromochloroacetonitrile

Fig. 1.18.6 Dibromoacetonitrile

Fig. 1.18.7 1,2,3-trichloropropane

27

1.19 Solvent Extraction and GC/MS Analysis of Haloacetic Acids in Water - GC/MS

■ ExplanationHaloacetic acids are known disinfection byproducts of thechlorine treatment of water. They were added to the waterquality control standards in May 2003. The standard valueswere set as 0.02 mg/L for chloroacetic acid, 0.04 mg/L fordichloroacetic acid, and 0.2 mg/L for trichloroacetic acid.These can be analyzed at high sensitivity using the SelectedIon Monitoring (SIM) method. Table 1.19.1 lists themonitor ions. Fig. 1.19.2 shows the SIM chromatograms ofstandard samples equivalent to 0.001 mg/L concentration inwater. Fig. 1.19.3 shows the calibration curves from 0.001to 0.1 mg/L. Fig. 1.19.4 shows the SIM chromatograms andquantitation results. 0.002 mg/L, which is 1/10 of the 0.02mg/L standard value, is used as the guideline for thequantitation lower limit required during the analysis of tapwater. The sensitivity achieved can satisfactorilyaccommodate this.

■ Analytical ConditionsInstrument-GC-ColumnColumn TemperatureCarrier GasInjection MethodInjection Inlet Temperature Injection Volume-MS-Interface Temperature Ion-Source TemperatureIonizationScan RangeScan IntervalSIMMonitor IonsSampling Interval

: GCMS-QP2010

: Rtx-1 (30 m × 0.25 mm I.D. df=1.0 µm): 35˚C (5 min) -15˚C/min-250˚C (5 min): He, 45 cm/s, Constant Linear Velocity Mode: Splitless (1 min.): 200˚C : 1 µL

: 230˚C : 200˚C : EI: m/z 35-350: 0.5 s

: See Table 1.19.1.: 0.2 s

Chloroacetic acid R=0.9999815

0.0 25.0 50.0 75.0 Conc Ratio0.0

0.5

1.0

1.5

2.0

2.5

3.0Area Ratio

Dichloroacetic acid R=0.9999871

0.0 25.0 50.0 75.0 Conc Ratio0.0

1.0

2.0

3.0

4.0

5.0

6.0

Area Ratio

Trichloroacetic acid R=0.9999956

0.0 25.0 50.0 75.0 Conc Ratio0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Area Ratio

Fig. 1.19.3 Calibration curves for haloacetic acid (0.001-0.1 mg/L)

Solvent Extraction, Derivatization, GC/MS Analysis

Sampling

50 mL water sample

Solvent extraction

Dehydration

Derivatization

GC/MS

Add 0.01 to 0.02 g sodium ascorbate per 1 mg residual chlorineReduce pH to 0.5 or below using sulfuric acid (1+1) and add 20 g sodium chloride.

4 mL methyl-t-butylether. Shake for 2 min.

Anhydrous sodium sulfate

0.2 mL diazomethane

Leave for 30-60 min

20 µL internal standard

Fig. 1.19.1 Haloacetic acid analysis flow

Chloroacetic acid

Dichloroacetic acid

Trichloroacetic acid

1,2,3-Trichloropropane

Quantitation ion

77

83

117

110

Reference ion

108

85

119

75

Table 1.19.1 Monitor ions

Chromatograms Sample name : 50 mL tap water +1 ppb

min

8,258

9.0 10.0 11.0 12

TIC8,258 TIC8,258 TIC

Chl

oroa

cetic

aci

d

Dic

hlor

oace

tic a

cid

Trich

loro

pro

pane

Tric

hlor

oace

tic a

cid

776

69

8.7

77

108

m/z: 77.00Type: TargetName: Chloroacetic acid

R.t.: 8.331Area: 257Conc.: 1.025 µg/L

m/z Intensity Ratio% Intensity Ratio%

Intensity Ratio%

108.00 97 38.00

862

1,404

10.0 10.3

83

85

m/z:83.00Type: TargetName: Dichloroacetic acid

R.t.: 9.925Area: 1425Conc.: 0.995 µg/L

m/z 85.00 885 62.00

440

411

11.0 11.7

117

119

m/z:117.00Type: TargetName: Trichloroacetic acid

R.t.: 11.309Area: 682

Conc.: 1.887 µg/L

m/z 119.00 673 99.00

Fig. 1.19.4 SIM chromatograms of tap water spiked with 0.001 mg/L standard

1,471

175

8.8

77

108

m/z: 77.00Type: TargetName: Chloroacetic acid

R.t.: 8.457Area: 471Conc.: 1.000 µg/L

m/z Intensity Ratio% 108.00 179 38.00

1,887

2,482

9.7 10.0 10.4

83

85

m/z:83.00Type: TargetName: Dichloroacetic acid

R.t.: 10.017Area: 909Conc.: 1.000 µg/L


438

420

11.7

117

119

m/z:117.00Type: TargetName: Trichloroacetic acid

R.t.: 11.391Area: 623Conc.: 1.000 µg/L


11,020

22,018

11.0 11.6

110

75

m/z:110.00Type: TargetName: Trichloropropane

R.t.: 11.291Area: 17160


Fig. 1.19.2 SIM chromatograms of a standard sample equivalent to 0.001 mg/L concentration in water

28

1.20 Solid-Phase Extraction, Derivatization, and GC/MS Analysis of Phenols in Water - GC/MS

■ ExplanationThis section introduces measurements of phenols in waterusing the solid-phase extraction, derivatization, and GC/MSanalysis method prescribed in the 2003 Ministry of Health,Labour and Welfare Notification No. 261 (partially revisedin 2005, Notification No. 125). The six measured phenolcomponents are phenol, 2-chlorophenol, 4-chlorophenol,2,4-dichlorophenol, 2,6-dichlorophenol, and 2,4,6-trichlorophenol. After the concentration of each componentis measured, it is converted to an equivalent concentrationof phenol. These are added together to determine theconcentration of phenols. The standard value is 5 µg/L.These measurements are essential, as phenol itself hasproblems of toxicity and chlorophenols produce anunpleasant odor, even at low concentrations.

■ Analytical ConditionsInstrument-GC-ColumnColumn TemperatureCarrier GasInjection MethodInjection Inlet Temperature Injection Volume-MS-Interface Temperature Ion-Source TemperatureIonizationScan RangeScan IntervalSIMMonitor IonsSampling Interval

: GCMS-QP2010

: Rtx-1 (30 m × 0.25 mm I.D. df=1.0 µm): 50˚C (2 min) -10˚C/min-250˚C (5 min): He, 45 cm/s, Constant Linear Velocity Mode: Splitless (Injection Pressure: 250 kPa): 250˚C : 1 µL

: 250˚C : 200˚C : EI: m/z 35-350: 0.5 s

: See Table 1.20.1.: 0.2 s

min

500,000

11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0

TIC

phen

ol

acen

apht

hene

d10

2-ch

loro

phen

ol

4-ch

loro

phen

ol

2,6-

dich

loro

phen

ol2,

4-di

chlo

roph

enol

2,4,

6-tr

ichl

orop

heno

l

Solid-phase Extraction, Derivatization, GC/MS Analysis

500 mL sample


Elution

Dehydration

Concentration

Derivatization

GC/MS

Styrene divinylbenzene vinylpyrrolidone copolymer solid-phase column

Reduce to pH 2 or below using HCl.

Deliver at 10-20 mL/min.

5 mL ethyl acetate

Backflush elution


4 mL aliquot

Blow pure nitrogen onto surface

Concentrate to approx. 0.8 mL

100 µL BSTFALeave for 1 hour. Add internal standard. Add ethyl acetate to make 1 mL.

ID#: 1m/z: 151.00 Name: Phenol

Correlation coefficient (R) = 0.999989Coefficient of determination (R2) = 0.999978Calibration curve: LinearInternal standard method Concentration

f (x) = 6.541340*x+0.009747

5.00.0 2.0

30

0.0

10

1 0.1 2 0.5 3 1.0 4 2.5 5 5.0

min

500,000

11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0

TIC

phen

ol

2-ch

loro

phen

ol

4-ch

loro

phen

ol

2,6-

dich

loro

phen

ol2,

4-di

chlo

roph

enol

acen

apht

hene

d10

2,4,

6-tr

ichl

orop

heno

l

phenol

2-chlorophenol

4-chlorophenol

2,4-dichlorophenol

2,6-dichlorophenol

2,4,6-trichlorophenol

acenaphthene d10

Selected ion

151, 166

185, 200

185, 200

219, 234

219, 234

253, 268

164, 162


Fig. 1.20.3 SIM chromatogram of tap water spiked with standards (equivalent to 0.5 µg/L concentration in water)

Fig. 1.20.4 Calibration curve for phenol

Fig. 1.20.1 Analysis flow

Fig. 1.20.2 SIM chromatogram of a 0.25 mg/L (each component) mixed standard sample (0.5 µg/L concentration in water)

29

1.21 Solid-Phase Extraction and GC/MS Analysis of 1,4-Dioxane in Water - GC/MS

■ Explanation1,4-dioxane is used as a variety of industrial solvents,including stripper for lacquer, resin, and paint. It is knownto be acutely toxic and inhaling a high concentration of itsvapor can cause fainting and nausea. Results of recentanimal testing indicate that oral exposure to lowconcentrations of 1,4-dioxane may be toxic or carcinogenic.1,4-dioxane is highly soluble in water, leading to concernsabout environmental pollution and adverse health effectsdue to effluent or discharged vapor. This section introducesan example of the analysis of 1,4-dioxane by solid-phaseextraction and GC/MS analysis. 1,4-dioxane-d8 internalstandard was added to a 200 mL water sample. This waspassed through a styrene divinylbenzene polymer solid-phase column and an activated carbon solid-phase column.The styrene divinylbenzene polymer solid-phase columnacts as a filter and the sample is retained in the activatedcarbon column. Only the activated carbon column issubsequently processed. It is first washed with purifiedwater and purged with pure nitrogen to dry it thoroughly.The sample is then eluted with acetone, concentrated byblowing with pure nitrogen gas, and subjected to GC/MS-SIM measurement.

■ Analytical ConditionsInstrument-GC-ColumnColumn Temperature

Carrier GasInjection MethodInjection Inlet Temperature Injection Volume-MS-Interface Temperature Ion-Source TemperatureIonizationScan RangeScan Interval-SIM-Monitor IonsSampling Interval

: GCMS-QP2010

: Rtx-1701 (30 m × 0.25 mm I.D. df=1.0 µm): 40˚C (2 min) -5˚C/min-90˚C -10˚C/min-250˚C (5 min)

: He, 45 cm/s, Constant Linear Velocity Mode: Split (10 : 1): 200˚C : 1 µL

: 250˚C : 200˚C : EI: m/z 35-350: 0.5 s

: m/z 88, 58, 96, 64: 0.2 s

Fig. 1.21.6 Quantitation results of spiked tap water sample

Mass chromatogram

min 9.0 10.0 11.0 11.9

TIC*1.00

96.00*1.00

88.00*1.00

1,4-Dioxane-d8

1,4-Dioxane

min 9.0 10.0 11.0 11.9

TIC*1.00

96.00*1.00

88.00*100.

1,4-Dioxane d8

1,4-Dioxane

Water Sample 200 mL sample Add internal standard solution (0.1 mg/mL 5 µL)

Solid-Phase ExtractionLinked styrene divinylbenzene polymer solid-phase column + activated carbon mini-column, sample flow rate 10 mL/min.

Washing, Dehydration Wash activated carbon column, dry with N2 gas

Elution 2 mL acetone

Concentration Blow pure N2 gas to concentrate to 1 mL

GC/MS SIM measurement

Quantitation graph

14,332

10.0 10.3

96*1.00

64*1.00

ID# : 1 m/z : 6.00Type : ISTDName : d8-1,4-Dioxane

R.T. : 9.795Area : 39707Conc. : 10.000 ppmm/z Intensity Ratio% Intensity Ratio% 64 32007 81.0

9,422

10.0 10.4

88*1.00

58*1.00

ID# : 2 m/z : 88.00Type : TargetName : 1,4-Dioxane

R.T. : 9.888Area : 28291Conc. : 5.878 ppmm/z 58 23178 82.0

#: 1 retention time: 9.8 (Scan#: 577)

m/z

100

40 50 60 70 80 90 100 110

46

64 96

#: 2 retention time: 9.9 (Scan#: 588)

m/z

100

40 50 60 70 80 90 100 110

45

58 88

1,4-dioxane

1,4-dioxane-d8

Quantitation ion

88

96

Reference ion

58

64

Fig. 1.21.2 Mass spectrum of 1,4-dioxane

Fig. 1.21.3 Mass spectrum of 1,4-dioxane-d8Fig. 1.21.4 Mass chromatograms of 0.01 mg/L standard sample

Fig. 1.21.5 Mass chromatograms of spiked tap water sample


Fig. 1.21.1 Analysis flow

30

1.22 Headspace Analysis of 1,4-Dioxane in Water- GC/MS

■ Explanation1,4-dioxane is a widely used solvent for waxes and dyes.Residues in the environment and effects on human healthare causes for concern. The World Health Organization(WHO) added 1,4-dioxane as a controlled substance duringa comprehensive revision of its quality guidelines fordrinking water. As most of the solid-phase extraction andGC/MS analysis process for 1,4-dioxane must be conductedmanually, it takes time to obtain analysis results. Inaddition, discrepancies can occur in measured results due todifferences in operator skill. The headspace–GC/MS methodis used to measure volatile organic compounds in water.This method automates all operations after the sample is putinto vials. The HS–GC/MS method permits quicker andeasier analysis than the solid-phase extraction method. Fig.1.22.1 shows the total ion chromatogram and mass spectrumof 1,4-dioxane. Fig. 1.22.2 shows the SIM chromatogramsof 1,4-dioxane at concentrations of 0.001 mg/L and 0.005mg/L.


-HS-Sample VolumeThermostat TemperatureNeedle TemperatureTransfer TemperatureCarrier Gas-GC-ColumnColumn Temperature-MS-Interface Temperature Ion-Source TemperatureScan IntervalMonitor IonsSampling Interval

: TurboMarix40+GCMS-QP2010

: 10 mL (3 g NaCl): 60˚C (30 min): 100˚C : 150˚C: He, 140 kPa

: Rtx-624 (60 m × 0.32 mm I.D. df=1.8 µm): 35˚C (1 min) -10˚C/min-230˚C (5 min)

: 220˚C : 200˚C : 0.3 s: m/z 88, 58: 0.2 s

Fig. 1.22.2 SIM Chromatograms of 1,4-dioxane (0.001 mg/L and 0.005 mg/L)

Fig. 1.22.1 Total ion chromatogram and mass spectrum

0.001 mg/L1,016

1,016

9.0 9.8

88

58

1 58.00 261 78.00 1 58.00 1446 77.00

0.005 mg/L2,253

2,253

9.0 9.8

88

58


R.T. : 9.327Area : 964

m# #/z Intensity Ratio%


R.T. : 9.305Area : 5099

m/z Intensity Ratio%

min

500,000

9.0 10.0 11.0 12.0 13.0 14.0 14.9

TIC

1,4-

Dio

xane # : 1 Retention time: 9.3 (Scan#: 162) No. of peaks: 18 Base peak: 88 (76195)

Spectrum: single 9.3 (162) Background: 9.3 (155)

m/z

100

40 60 80 100 120 140 160 180 200 220 240

43

58

73

88

31

1.23 Simultaneous Analysis of 1,4-Dioxane and VOCs in Water using Purge&Trap GC/MS- GC/MS

■ ExplanationSolid-phase extraction and GC/MS is used as the analysismethod for 1,4-dioxane in water. As most of the solid-phaseextraction process must be conducted manually, it takestime to obtain analysis results. While not conforming to theofficial method, HS-GC/MS or P&T-GC/MS can also beused for the analysis of 1,4-dioxane. P&T-GC/MS, inparticular, permits high-sensitivity analysis of compoundsthat are highly soluble in water. Fig. 1.23.1 shows thechromatogram of a 1 µg/L standard solution made byadding 1,4-dioxane and methyl-t-butylether to standardsamples of 23 VOCs. Adequate separation was achieved forquantitation. Fig. 1.23.3 shows the SIM chromatograms for0.1 µ g/L 1,4-dioxane. Satisfactory repeatability wasachieved for both 1,4-dioxane and the other VOCs. Table1.23.2 shows the repeatability for 0.1 µ g/L 1,1-dichloroethylene, chloroform, 1,4-dioxane, andtetrachloroethylene.


-P&T-TrapPurge TimePurge Flow RateAdsorption/Desorption TimeSample Volume-GC-ColumnColumn Temperature

-MS-Interface Temperature Ion-Source TemperatureIonization

: AQUA PT 5000J (Tekmar) +GCMS-QP2010

: GL Trap: 7 min Preheat Temperature: 60˚C : 40 mL/min Dry Purge Time: 7 min: 3 min Temperature: 200˚C: 5 mL

: AQUATIC2 (60 m × 0.32 mm I.D. df=1.8 µm): 40˚C (7 min) -3˚C/min-80˚C

-15˚C/min-220˚C (5 min)

: 220˚C: 200˚C: EI

Fig. 1.23.3 SIM chromatograms for 0.1 µg/L 1,4-dioxane

Quantitation graph

467

18.0 18.8

88*1.00

58*1.00


R.T. : 18.274Area : 3016

min

1,500,000

10.0 20.0 29.0

TIC

12 3 4 5 6

7 8

9

10 1112 13 14 15

16

17181920

21

22

23

24

14

1,4-Dioxane

131211

min

10,000

16.0 17.0 18.0 19.0

1,1-DichloroethyleneChloroform1,4-DioxaneTetrachloroethylene.

1

0.0950.0930.1190.117

2

0.0920.0920.1170.118

3

0.0950.0920.120.118

4

0.0930.0910.1190.119

5

0.0920.0890.1050.12

Average

0.0940.0920.1160.119

1.51.455.51.04

CV(%)

Peak No. 123456789

101112131415161718192021222324

Compound1,1-DichloroethyleneDichloromethaneMethyl-t-butyl ethertrans-1,2-Dichloroethylenecis-1,2-DichloroethyleneChloroform1,1,1-TrichloroethaneCarbontetrachlorideBenzene1,2-DichloroethaneTrichloroethylene1,2-DichloropropaneBromodichloromethane1,4-Dioxanecis-1,3-DichloropropeneToluenetrans-1,3-Dichloropropene1,1,2-TrichloroethaneTetrachloroethyleneDibromochloromethanem,p-Xyleneo-XyleneBromoformp-Dichlorobenzene

96847396968397

1177862

13063838875917583

166129106106173146

SIM61865761618599

119774995628558

11092

11097

164127105105171148

9849

98984761

1215264

132

47

85129131

9191

175

Table 1.23.1 Table of monitor ions

Table 1.23.2 Repeatability (0.1 µg/L concentration)

Fig. 1.23.2 Enlarged chromatogram

Fig. 1.23.1 SIM chromatogram for 25 VOCs

32

1.24 Analysis of the Components Controlled under the Waterworks Lawwith a Single Column (1) - GC/MS

■ ExplanationThe 2003 partial revisions to the Japanese Waterworks Lawadded 1,4-dioxane and haloacetic acids as items measuredby GC/MS and added water-quality control standards forchloral hydrate and dichloroacetonitrile. As differentcapillary columns are normally used to measure each ofthese components, the columns have to be changed over.The vacuum should remain as unbroken as possible to

■ Analytical ConditionsInstrumentColumn-GC-Column TemperatureCarrier GasInjection Inlet TemperatureInjection MethodInjection Volume

: GCMS-QP2010: Rtx-5MS (30 m × 0.25 mm I.D. df=1.0 µm)

: 40˚C (2 min) -10˚C/min- 250˚C (3 min): He, 47.6 cm/s, Constant Linear Velocity Mode: 250˚C: Splitless (1 min.) : 1 µL

obtain data with good repeatability. Replacing the column asseldom as possible is desirable to obtain the data morepromptly and more reliably. This section describes how tomeasure phenols, haloacetic acids, formaldehyde, and 1,4-dioxane using a single column (Rtx-5MS, 30 m × 0.25 mmI.D. df=1.0 µm).

PFBOA-Formaldehyde

-MS-Interface Temperature Ion-Source TemperatureIonizationScan RangeScan Interval

: 250˚C : 200˚C : EI: m/z 45-250: 0.5 s

min

6,232,201

10.0 11.0 12.0 13.0 14.0 15.0 15.5

TIC

1/ F

orm

alde

hyde

-PF

BO

A

2/ 1

-Chl

orod

ecan

e

15,652

2,484

10.9

181

195

1 195.00 2207

ID# : 1 m/z : 181.00Type : TargetName : Formaldehyde

R.T. : 10.408Area : 34592

m# /z Intensity



: 50˚C (1 min) -10˚C/min- 250˚C (3 min): He, 46.6 cm/s, Constant Linear Velocity Mode: 250˚C: Splitless (1 min.) : 1 µL

Fig. 1.24.1 Total ion chromatogram Fig. 1.24.2 Mass chromatograms (SCAN, 0.01 mg/L, equivalent to 0.001 mg/L concentration in water*)


: 250˚C : 200˚C : EI: m/z 60-300: 0.5 s

TMS-Phenols

33



: 35˚C (1 min) -10˚C/min- 230˚C (3 min): He, 48 cm/s, Constant Linear Velocity Mode: 230˚C: Splitless (1 min.) : 1 µL

Diazomethane-derivatized Haloacetic Acids

-MS-Interface Temperature Ion-Source TemperatureIonizationScan RangeScan IntervalSIM Interval

: 230˚C : 200˚C : EI: m/z 55-260: 0.5 s: 0.2 s

min

9,532,182

9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0

TIC

1/ p

heno

l

2/ 2

-chl

orop

heno

l

3/ 4

-chl

orop

heno

l

4/ 2

,6-d

ichl

orop

heno

l

5/ 2

,4-d

ichl

orop

heno

l

6/ 2

,4,6

-tric

hlor

ophe

nol

7/ a

cena

phth

ene

d10

13,308

48,089

9.9

166

151

8,182

19,550

12.0 12.4

200

185

8,182

19,550

12.9

200

185

3,064

9,664

14.0 14.7

234

219

3,064

9,664

14.8

234

219

1,862

7,451

16.0 16.5

268

253

1 151.00 44619

ID# : 1 m/z : 166.00Type : TargetName : phenol

R.T. : 9.435Area : 27020

m# /z Intensity 1 185.00 11057

ID# : 2 m/z : 200.00Type : TargetName : 2-chlorophenol

R.T. : 11.970Area : 9072

m# /z Intensity 1 185.00 18282

ID# : 3 m/z : 200.00Type : TargetName : 4-chlorophenol

R.T. : 12.405Area : 16962

m# /z Intensity

1 219.00 8852

ID# : 4 m/z : 234.00Type : TargetName : 2,6-dichlorophenolR.T. : 14.212Area : 5756

m# /z Intensity 1 219.00 8771

ID# : 5 m/z : 234.00Type : TargetName : 2,4-dichlorophenolR.T. : 14.377Area : 6221

m# /z Intensity 1 253.00 6551

ID# : 6 m/z : 268.00Type : TargetName : 2,4,6-trichlorophenolR.T. : 16.095Area : 3991

m# /z Intensity

min

27,712,779

6.0 7.0 8.0 9.0

TIC

1/ c

hlor

oace

tic a

cid

2/ d

ichl

oroa

cetic

aci

d

3/ tr

ichl

oroa

cetic

aci

d

4/ 1

,2,3

-tric

hlor

opro

pane

15,721

45,668

6.0

108

77

167,235

125,204

7.0 7.5

83

85

29,567

27,165

9.0

117

119

1 77.00 36803

ID# : 1 m/z : 108.00Type : TargetName : chloroacetic acid

R.T. : 5.523Area : 21618

m# /z Intensity

1 119.00 23685

ID# : 3 m/z : 117.00Type : TargetName : trichloroacetic acid

R.T. : 8.576Area : 48207

m# /z Intensity

1 85.00 101492

ID# : 2 m/z : 83.00Type : TargetName : dichloroacetic acid

R.T. : 7.046Area : 296488

m# /z Intensity


Fig. 1.24.3 Total Ion Chromatogram Fig. 1.24.4 Mass chromatograms (SCAN, 0.05 mg/L, equivalent to 0.000125 mg/L concentration in water*)

Fig. 1.24.5 Total ion chromatogram Fig. 1.24.6 SIM Chromatograms (0.0225 mg/L chloroacetic acid methyl ester; dichloroacetic acid methyl ester, equivalent to 0.0018 mg/L concentration in water*; 0.0075 mg/L trichloroacetic acid methyl ester, equivalent to 0.0006 mg/L concentration in water*)

34


■ Analytical ConditionsInstrumentColumn

-GC-Column Temperature

Carrier GasInjection Inlet TemperatureInjection MethodInjection Volume


: 40˚C (1 min) -15˚C/min- 100˚C -20˚C/min- 250˚C (3 min)

: He, 47.6 cm/s, Constant Linear Velocity Mode: 230˚C: Splitless (1 min.) : 1 µL

1,4-Dioxane


: 230˚C : 200˚C : EI: m/z 40-120: 0.5 s

min

1,779,042

6.0 6.8

TIC

1,4-

diox

ane-

d8

1,4-

diox

ane

4,365

12,682

5.0 5.8

88

58

1 58.00 3470


R.T. : 5.367Area : 11119

m# /z Intensity

* "Equivalent concentration in water" is the value after pretreatment according to the method prescribed in Ministry of Health, Labour and Welfare Notification No. 261, 22 July 2003 (partially revised in Ministry of Health, Labour and Welfare Notification No. 191, 30 March 2006).

Fig. 1.24.7 Total Ion Chromatogram Fig. 1.24.8 Mass chromatograms (SCAN, 0.01 mg/L, equivalent to 0.00005 mg/L concentration in water*)

35

1.25 Analysis of Volatile Organic Compounds (VOCs) in Tap Water (1)- Purge & Trap GC/MS

■ ExplanationThe purge trap method involves purging volatile organiccompound that exists in water using helium or nitrogen gas,holding it in a trap tube, then quickly heating it to induct itinto a GC/MS column. Nearly all the volatile constituentsincluded in a 5 mL sample are concentrated in the trap tubeto enable highly sensitive analysis.Figure 1.25.1 is SIM chromatograms of the 23 constituentcompounds targeted and p-bromofluorobenzene (IS) ofindividual 0.1 µg/L concentration. The Table 1.25.1 showsthe names of the targeted compounds and the SIM selectedions.

References(1) Drinking Water Test Method & Explanation,

(2001 Edition) Japan Water Works Association(2) Environmental Water Analysis Manual,

Environmental Science Research Group volume(3) New Wastewater Standards and Other Analysis

Methods,

Trap TubeSample Purge TimeDesorption

: GL Trap 1: 8 min: 220˚C, 6 min

Fig. 1.25.1 Measuring example of 0.1 µg/L added water

Column

Column Temperature

Carrier Gas

Shimadzu GCMS

P&T: Tekmar Purge & Trap System


: AQUATIC(60 m × 0.32 mm I.D.df=1.8 µm)

: 35˚C (5 min) -6˚C/min -90˚C-10˚C/min -220˚C (3 min)

: He 90 kPa

36

1.25 Analysis of Volatile Organic Compounds (VOCs) in Tap Water (2)- Purge & Trap GC/MS

Fig. 1.25.2 Purge & trap GC/MS system

123456789101112

ID1,1-DichloroetheneDichloromethanetrans-1,2-Dichloroethenecis-1,2-DichloroetheneChloroform1,1,1-TrichloroethaneTetrachloromethane1,2-DichloroethaneBenzeneTrichloroethene1,2-DichloropropaneBromodichloromethane

Name96,6184,8696,6196,6183,8597,99117,11962,6478,77130,13263,6283,85

SIM Selected Ions1314151617181920212223

IDcis-1,3-DichloropropeneToluenetrans-1,3-Dichloropropene1,1,2-TrichloroethaneTetrachloroetheneDibromochloromethanem,p-Xyleneo-XyleneBromoformp-Bromofluorobenzene(IS)p-Dichlorobenzene

Name75,11092,9175,11097,99166,164129,127106,91106,91173,175174,176146,148

SIM Selected Ions

Table 1.25.1 SIM selected ions

37

1.26 Simultaneous Analysis of Monitored VOCs in Water using Purge&Trap GC/MS - GC/MS

■ ExplanationIn the February 2004 review of environmental standardsrelated to environmental water contamination by theJapanese Central Environmental Council added 5 newmonitored items –– vinyl chloride monomer, 1,4-dioxane,epichlorohydrin, total manganese, uranium –– to make atotal of 27 monitored components. Of these new items, 1,4-dioxane is measured by solid-phase extraction and GC/MS,while vinyl chloride monomer and epichlorohydrin areanalyzed using Purge&Trap GC/MS. Table 1.26.1 lists thecomponent names and standard values for the monitoredVOCs that are measured by Purge&Trap GC/MS.Simultaneous analysis of 25 VOCs (vinyl chloride monomerand epichlorohydrin plus 23 others) was conducted withoutcryofocus. Fig. 1.26.1 shows the total ion chromatogram(TIC) of the measurements in scan mode. Epichlorohydrinhas the lowest standard value, just 0.0004 mg/L. Fig. 1.26.2shows the SIM chromatograms for vinyl chloride monomerand epichlorohydrin standard samples prepared to aconcentration equivalent to 1/10 of this standard value(0.00004 mg/L for each component).


-P&T-TrapTransfer Line TemperatureValve Oven TemperatureMount Temperature Purge TimePurge Flow RateAdsorption/Desorption TimeBake TemperatureCryofocus-GC-ColumnColumn Temperature

-MS-Interface Temperature Ion-Source TemperatureIonizationScan RangeScan Interval-SIM-Monitor IonsSampling Interval

: AQUA PT 5000J (Tekmar) +GCMS-QP2010

: GL Trap: 180˚C: 180˚C: 60˚C Purge Temperature: 30˚C : 1.5 min Preheat Temperature: 35˚C : 40 mL/min Dry Purge Time: 0.7 min: 1 min Temperature: 180˚C: 220˚C Bake Time: 53 min: OFF

: Rtx-1 (60 m × 0.32 mm I.D. df=5.00 µm): 35˚C (20 min) -2˚C/min-62˚C

-10˚C/min-100˚C-20˚C/min -200˚C-15˚C/min-230˚C (6 min)

: 230˚C: 200˚C: EI: m/z 35-350: 0.5 s

: See Table 1.26.1.: 0.2 s

2,067

5.0

62*1.00

64*1.00

ID# : 1 m/z : 62.00Type : TargetName : Vinyl chloride monomer

R.T.: 4.831Area : 13045

# m/z Intensity Ratio %

# m/z Intensity Ratio %

1 64.00 4035 30.93

1,935

57*1.00

49*1.00

ID# : 5 m/z : 57.00Type : TargetName : Epichlorohydrin

R.T.: 35.992Area : 466

1 49.00 47 10.09

min

250

36.0 36.5

min

10,000,000

10.0 20.0 30.0 40.0 48.0

min

420,000

4.0 5.0 6.0

62.00*1.00

64.00*3.00

min

200,000

35.0 36.0 37.0

57.00*10.0

49.00*25.0

1. Vinyl chloride monomer 5. Epichlorohydrin

21

1

5

43

6

7

8

5

9

TIC*1.00 TIC*1.00

TIC*1.00

4

ID#

1

2

3

4

5

6

7

8

9

Name

Vinyl chloride monomer

trans-1,2-Dichloroethylene

Chloroform

1,2-Dichloropropane

Epichlorohydrin

Toluene

m,p-Xylene

o-Xylene

1,4-Dichlorbenzene

Standard value(mg/L)

0.02

0.04

0.06

0.06

0.0004

0.6

0.4

0.2

Ret.Time

4.78

15.38

22.61

34.68

35.96

39.52

42.51

43.06

45.28

62

96

83

63

57

92

106

106

146

SIM ion

64

61

85

65

49

91

91

91

148

98

47

62

105

105

Table 1.26.1 Monitored VOCs and monitor ions

Fig. 1.26.1 Total ion chromatogram (TIC) of 25 VOCs (scan mode) Fig. 1.26.2 SIM chromatograms of 0.04 µg vinyl chloride monomer and epichlorohydrin

38

1.27 Analysis of Musty Smelling Components in Tap Water (P/T Method) (1) - GC/MS

■ ExplanationJapanese tap water has an established reputation in the areaof quality as drinking water; however, in recent years, it hasa musty odor depending on the season. And the substancesthat cause this musty odor are known to be 2-methylisoborneol and geosmin. The threshold value for theodors of these compounds is approximately several ng/L,which is low, and cannot be detected in source state byGC/MS analysis, so the purge trap method, as shown in thedrinking water test method, is used to concentrate thecompounds for analysis by GC/MS. This purge trap methodinvolves forcing the targeted compound into a gas phaseusing aeration, holding this gas phase in a concentrationtube filled with adsorbent, then forcing out of theconcentration tube by heating.

References (1) Drinking Water Test Method & Explanation,

(2001 Edition) Japan Water Works Association(2) Environmental Water Analysis Manual,

Environmental Science Research Group volume


Fig. 1.27.1 Analysis example of musty odor 0.001 µg/L(upper: 2-MIB, lower: geosmin)

Fig. 1.27.2 Calibration curves (0.01~0.02 µg/L)(upper: 2-MIB, lower: geosmin)

P&T: AQUA PT5000J

Shimadzu GCMS-QP2010

Trap TubeSample Purge TimeForce Out

: GL Trap 1: 12 min: 220˚C, 6 min

Column

Column Temperature

Carrier gas

: Inert Capl (30 m × 0.32 mm I.D.df=0.4 µm)

: 35˚C (6 min) -10˚C/min -220˚C (13 min)

: He 120 kPa

39

CH3 CH3

CH3

CH3

CH3

OHCH3

OH

2-Methyl isoborneol :m/z 95,108 Geosmin:m/z 112.126

Fig. 1.27.4 Principle diagram of purge & trap method

Fig. 1.27.3 Structures of 2-MIB and geosmin

1.27 Analysis of Musty Smelling Components in Tap Water (P/T Method) (2) - GC/MS

1.28 Analysis of Musty Smelling Components in Tap Water (HS Method) - GC/MS

40

■ ExplanationJapanese tap water has an established reputation in the areaof safety as drinking water; however, musty smellingcomponents in dam, lake and river surface water that is thesource of tap water has become a summer problem, whichis being combated through the use of activated carbon. Andthe substances that cause this musty odor are 2-methylisoboneol (2-MIB) and geosmin produced via blue-green algae and actinomycetes. The threshold value for theodors is several ng/L, which is an extremely lowconcentration, so the solid-phase extraction & GC/MS orpurge & trap GC/MS is used to make measurements. TheDrinking Water Test Method was revised in September2001 with the addition of a straightforward headspaceGC/MS method to the conventional method. This pageintroduces considered results concerning the quantificationaspect of this method.

References (1) Shimadzu Application News, No. M204(2) Drinking Water Test Method & Explanation

(2001 Edition)Japan Water Works Association

■ Analytical ConditionsHS

GC

Sample VolumeSample TemperatureSample Shaker

: 10mL + NaCl 3g: 80˚C (30 min): ON

MS

IonizationSIM Monitor Mass

: EI: 2-MIB (95, 107),

Geosmin (112, 125)

Column

Column Temperature

Injection Inlet TemperatureCarrier Gas

Injection Method

: Rtx-5 MS (30 m × 0.25 mm I.D. df=0.25 µm)

: 35˚C(2 min)-15˚C/min -250˚C(10 min)

: 230˚C: He 100 kPa (High-Pressure

Injection of 300 kPa): Direct injection

min

intensity

90

50010001500200025003000350040004500500055006000

95.00*1.00

107.00*1.00

min

intensity

90

5000

10000

95.00*1.00

107.00*1.00

0.001 µg/L 0.005 µg/L

min

intensity

110

500100015002000250030003500400045005000

112.00*1.00

125.00*1.00

(A) 2-MIB

(B) Geosmin

0.001 µg/L 0.005 µg/Lmin

intensity

110

5000

10000

15000

112.00*1.00

125.00*1.00

Fig. 1.28.1 SIM chromatograms

Conc.

Area

5[*10^1]

8

[*10^4]

Conc.

Area

5[*10^1]

8

[*10^4]

(A) 2-MIB (B) Geosmin

r=0.9996 r=0.9997

Fig. 1.28.2 Calibration curves (0.001-0.050 µg/L)

1.29 Analysis of Musty Smelling Components in Tap Water (SPME Method) - GC/MS

41

■ ExplanationJapanese tap water has established reputation in the area ofsafety as drinking water; however, musty smellingcomponents in dam, lake and river surface water that is thesource of tap water has become a summer problem, whichis being combated through the use of activated carbon. Andthe substances that cause this musty odor are 2-methylisoborneol (2-MIB) and geosmin produced via blue-green algae and actinomyces. The threshold value for theodors is several ng/L, which is an extremely lowconcentration, so concentrating the sample in pretreatmentis important. In the Drinking Water Test Method, the solid-phase extraction & GC/MS and purge & trap GC/MS hadbeen adapted as measurement methods. The DrinkingWater Test Method was revised in September 2001 with theaddition of a straightforward headspace GC/MS methodNevertheless, the extraction operation of the solid-phaseextraction GC/MS method is problematic in that it takes alot of process time because the operation is cumbersomeand a large amount of organic solvent has to be used.Further, the purge & trap GC/MS method requires anexpensive system and machine maintenance is difficult. Whereas the solid-phase micro extraction method (SPME)is a pretreatment method that can extract the organiccompound from the headspace of the liquid or solid sample,concentrate it, apply thermal desorption in the vaporizingchamber of the gas chromatograph, and induct it into thecolumn. This method is gathering attention because it doesnot use organic solvents required by conventional solid-

phase extraction, and operation is simple and automationpossible.

References (1) Shimadzu Application News, No. M204(2) Shimadzu Application News, No. M209(3) Drinking Water Test Method & Explanation (2001 Edition)

Japan Water Works Association

■ Analytical ConditionsSPME

GC

SPME FiberSample VolumeSample Temperature

: PDMS/DVB65 µm: 10 mL + NaCl 3g: 80˚C (30 min)

Column

Column TemperatureInjection Inlet TemperatureCarrier GasInjection Method

: DB-5(30 m × 0.25 mm I.D. df=0.25 µm)

: 40˚C (3 min) -15˚C/min -250˚C (3 min): 230˚C: He 100 kPa: Splitless (3 min)

MS

IonizationSIM Monitor Mass

: EI: 2-MIB (95, 107)

Geosmin (112, 125)

ID#:1 m/z:95.00 Name:2-MIBf(x)=22364490.302279*x+5991.570697Correlation coefficient(R)=0.999499

5[*10^-2]

1

[*10^6]

#1234

Concentration (µg/L)0.0010.0100.0200.050

Area26133

246730434120

1128506

(1)2-MIBID#:2 m/z:112.00 Name:Geosminf(x)=64559563.075706*x-17585.304252Correlation coefficient(R)=0.999714

5[*10^-2]

3

[*10^6]

#1234

Concentration (µg/L)0.0010.0100.0200.050

Area66289

64125312244013227040

(2)Geosmin

Fig. 1.29.2 Calibration curves (0.001-0.050 µg)

min

intensity

11.0 11.1 11.2 11.3 11.4 11.50

5000

10000

15000

20000

25000

30000

35000

40000

45000

50000

95.00*1.00

107.00*1.00

2-M

IB

min

intensity

11.0 11.1 11.2 11.3 11.4 11.50

50000

100000

150000

200000

250000

300000

350000

400000

95.00*1.00

107.00*1.00

2-M

IB

(1)2-MIB

0.010 µg/L 0.010 µg/L

min

intensity

14.5 14.6 14.7 14.8 14.9 15.00

50001000015000200002500030000350004000045000500005500060000

112.00*1.00

182.00*1.00

geos

min

min

intensity

14.5 14.6 14.7 14.8 14.9 15.00

50000100000150000200000250000300000350000400000450000500000550000600000

112.00*1.00

182.00*1.00

geos

min

(2)Geosmin

0.010µg/L 0.010 µg/L

Fig. 1.29.1 SIM chromatograms

42

1.30 Headspace–GC/MS Analysis of Fishy Smelling Components in Water - GC/MS

■ ExplanationIn recent years, not only safety but also pleasantness isbeing demanded of drinking water. The pleasantness ofdrinking water can be adversely affected by a number offactors, foul odor being one such factor. The componentsmeasured here are the unsaturated aldehydes produced bygolden algae, heptadienal (2E,4Z and 2E,4E) and decadienal(2E,4Z and 2E,4E), that are causes of fishy odors in water.Due to the high vapor pressure of these components, theyare normally measured using Purge&Trap GC/MS. Thissection describes the measurement of these components byheadspace–GC/MS. Fig. 1.30.1 shows the total ionchromatogram and mass spectra of 2E,4Z and 2E,4Eheptadienal (M.W. 110) and 2E,4Z and 2E,4E decadienal(M.W. 152). As the 2E,4Z and 2E,4E isomers exhibitidentical mass spectra, just the 2E,4Z is shown here. Fig.1.30.2 shows the SIM chromatograms of 0.050 µg/L 2E,4Zheptadienal and 2E,4Z decadienal. The analysis of tracelevels of these components is required, as no standardvalues are set for them. Headspace–GC/MS is adequate formeasuring these components as it is able to detect them at0.050 µg/L concentrations.


-HS-Sample VolumeThermostat TemperatureInjection TimeNeedle TemperatureTransfer TemperatureAgitationCarrier Gas-GC-ColumnColumn Temperature

Injection Inlet Temperature-MS-Interface Temperature Ion-Source TemperatureMonitor Ions

: TurboMarix 40(with vial-shaker and PPC) + GCMS-QP2010

: 10 mL (3 g NaCl): 80˚C (30 min): 1 min: 100˚C: 200˚C: ON: He, 150 kPa (Injection Pressure: 250 kPa)

: Rtx-5MS (30 m × 0.25 mm I.D. df=1.0 µm): 35˚C (1 min) -10˚C/min-100˚C -5˚C/min -

250˚C (3 min): 230˚C

: 200˚C: Heptadienal (110, 81)Decadienal (152, 81)

min

20,000,000

10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0 19.0 20.0 21.0

TIC

2E,4

Z-H

epta

dien

al

2E,4

E-H

epta

dien

al

2E,4

Z-D

ecad

iena

l

2E,4

E-D

ecad

iena

l

m/z

100

30 50 70 90 110

39 5367

81

95110

m/z

100

30 50 70 90 110 130 150

4155 67

81

95108 123 137 152

Mass spectrum(heptadienal)

Mass spectrum(decadienal)

2,082

8,795

10.4 10.9

110

81

1,183

15,300

18.9

152

81

2E,4Z-Heptadienal

2E,4Z-Decadienal

Ratio% 439.14 1 81.00 15383

ID# : 1 m/z : 110.00Type : TargetName : 2E,4Z-Heptadienal

R.T. : 10.622Area : 3503

m# /z Intensity

Ratio% 1624.08 1 81.00 42957

ID# : 3 m/z : 152.00Type : TargetName : 2E,4Z-Decadienal

R.T. : 18.715Area : 2645

m# /z Intensity

Fig. 1.30.2 SIM chromatograms (0.050 µg/L) Fig. 1.30.1 Total ion chromatogram and mass spectra

43

1.31 Analysis of Acrylamide in Water (1) - GC,GC/MS

■ ExplanationIn 1974 the Environmental Sanitation Bureau of the JapaneseMinistry of Health, Labour and Welfare prescribed that, as ajudgment criteria for well drinking water, acrylamide would beundetectable beyond the detection limit of 0.1ppm; however,this prescription was abrogated in the water quality standardestablished in December 1993. Nevertheless, in March 2000, thisissue was raised again as an evaluation item in the testmethod guideline for evaluating tap water chemicals by thewaterworks office of the water supply & environmentalsanitation department in the Environmental Health Bureau ofthe Ministry of Health, Labour and Welfare. In the 1993volume of the Drinking Water Test Method a packed-columnanalysis method was employed to analyze 2,3-Dibromopropionamide (2,3-DBPA) obtained throughbromination of acrylamide; however, as 2,3-DBPA wasunstable, the following amendment was introduced to the 2001volume.The test method requires the bromination of acrylamide intest water using potassium bromate in a situation wherebromide ions exist, followed by the extraction of thesynthesized 2,3-DBPA using ethyl acetate, and itsconversion to 2-Bromopropeneamide (2-BPA) usingtriethylamine, so that a GC-ECD can measure it. Note thatthe GC/MS method was added and employed in the 2001volume.

ReferenceDrinking Water Test Method & Explanation(2001 Edition)Japan Water Works Association

■ Analytical ConditionsColumn

Column TemperatureInjection Inlet TemperatureDetector TemperatureCarrier GasInjection MethodInjection Volume

: DB-WAX(30 m × 0.25 mm I.D. df=0.25 µm)

: 50˚C -10˚C/min -200˚C: 250˚C: 250˚C (ECD): He 300 kPa: Split (1:20): 1 µL

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

Position of acrylamide Br

Fig. 1.31.1 Chromatogram of sample extracted from tap water

0.0

2.0

4.0

6.0

8.0

10.0

12.0

14.0

Acrylamide Br

Fig. 1.31.2 Chromatogram of sample extracted from tap water with acrylamide added (Equivalent to 0.1µg/L concentration in water)

44

14 15 16 17 18min

0

5000000 TIC*1.0079.00*5.0081.00*5.00

15.800

Fig. 1.31.7 NCI chromatograms of acrylamide extracted from test water

Retension time: 15.8 (Scan #:216)100

30 50 70 90 110 130 150 170 190 210 230 250 270 290m/z

79

Retension time: 15.8 (Scan #:216)

Fig. 1.31.5 NCI mass spectrum

Sample

Derivatization

Solvent extraction

Dehydration

Concentration

Alkali addition

GC/NCI-MS

Reduce pH to 1 or below using sulfuric acid (1+5)

Potassium bromate solutionSodium thiosulfate solution

Ethyl acetate


Triethylamine

Fig. 1.31.3 Pretreatment flow

15 16

100000

150000

50000

0

79/81ID#: 1 m/z: 79.00Type: TargetName: 2-Bromo proplyamideR.T.: 15.794Area: 310069Conc.: 0.251µg/L

#1

m/z81.00

Intensity294742

Ratio %95.00

Fig. 1.31.8 Quantifying results for sample

14 15 16 17 18min

4000000350000030000002500000200000015000001000000500000

0

TIC *1.0079.00 *2.00

15.7

95

Fig. 1.31.6 NCI mass chromatogram for 0.5µg/L

O

NH2 + Br2 – BrNH2

Br

Br

O

Br

O

NH2

Fig. 1.31.4 Derivatization reaction

1.31 Analysis of Acrylamide in Water (2) - GC,GC/MS

■ ExplanationNegative chemical ionization (NCI) is effective in GC/MSbecause of its selectivity and high sensitivity for halogencompounds. This data introduces examples of analysisusing NCI-GC/MS.

References(1) Shimadzu Application News, No. M199(2) Drinking Water Test Method & Explanation



MS

GC

IonizationScan RangeMonitored Mass

: NCI (Isobutane): m/z 35-400: 81, 79

Column

Column TemperatureInjection Inlet TemperatureCarrier GasInjection MethodInjection Volume

: ZB-WAX (30 m × 0.25 mm I.D.df=0.25 µm)

: 60˚C (2 min) -10˚C/min -200˚C (2 min): 200˚C: He 300 kPa: Splitless (2.0 min): 1 µL

1.32 Analysis of Ethylenediamine Tetraacetic Acid (EDTA) - GC/MS

45

■ ExplanationIn July 2001 the Japanese Drinking Water Test Method wasamended with the addition of a measuring method forethylenediamine tetraacetic acid (EDTA). EDTA is widelyused in daily necessities including agricultural produce andfood additives as well as being used in many industrialgoods, plating, pharmacy items and in the water softeningprocess, etc. Hardly any of the discharged EDTAdecomposes in the environment, and is thought to exist inthe form of a metal chelate, which suggests that it is presentin environment water, albeit in miniscule amounts. Results of animal tests show that, although slender, EDTAis suspected of being toxic to mankind, which has led FAOand WHO to set a guideline value for EDTA to 0.6 mg/L:an ADI of 1.9 mg/kg of body weight/day allocating 1 % todrinking water. While in the Drinking Water Test Methodfor EDTA in water, the quantitative lower limit is set as 0.5µg/L. Sample is concentrated 100 times in the pretreatmentoperation, so the quantitative lower limit of 0.05 mg/L ismet for the requirement of actually measuring a testsolution, which means that sensitivity is not a problem.Fig.1.32.1 shows the analysis flow.

References(1) Shimadzu Application News, No. M207(2) Drinking Water Test Method & Explanation



MS

GC

IonizationScan RangeMonitored Mass

: EI: m/z 35 - 450: EDTA 174, 289, 348

CyDTA (IS) 343, 402

Column

Column Temperature

Injection Inlet TemperatureCarrier GasInjection MethodInjection Volume

: Solgel 1 (30 m × 0.25 mm I.D.df=0.25 µm)

: 60˚C (2 min) -15˚C/min -270˚C(4 min)

: 250˚C: He 100 kPa : Splitless (1.0 min/250kPa): 1µL

ET

DA

IS(C

yDT

A)

239,873 343.15

176,159 402.15

289.10

174.10

348.10

5,437

1,621

1,070

SIM Chromatogram EDTA 20ppb-1

min15.0 16.0 17.0 18.0

Fig. 1.32.5 SIM chromatograms for 0.02mg/L standard sample

#: 2 Retention time: 17.6 (Scan #: 436)

m/z

100

30 50 70 90 110 130 150 170 190 210 230 250 270 290 310 330 350 370 390

41

42

6781

96

102

112 128142 160

168

182

200213 228

240

254 269 283 297 311

329

343

370

402

Fig. 1.32.3 CyDTA (IS) mass spectrum

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

m/z

100

30 50 70 90 110 130 150 170 190 210 230 250 270 290 310 330 350

41

45

56 74 97

116128

146

157

174

188

208 235 264 275

289

296 316348

350

Fig. 1.32.2 EDTA mass spectrum

100mL of sample water

Vacuum concentrating to 2mL

Desiccate by N2 gas

Leave for 1hr at 80°C

Shaking & centrifuging

GC/MS measuring

IS (CyDTA 0.1mg/mL) 50µL

50µL of formic acid

15% BF3 - MeOH 1mL

3mL phosphate buffer (pH 7)1mL dichloromethane

Dichloromethane liquid layer


HOHO

O

O

BF3

CH3OH

O

O

O O

NN

O

O

O

O

O

OHOHN

N

Fig. 1.32.4 Derivatization reaction

46

1.33 TOC Analysis of Chlorinated Isocyanuric Acid - TOC

■ ExplanationDue to revisions to the water quality standards in theJapanese Waterworks Law, potassium permanganateconsumption quantity was replaced by total organic carbon(TOC) as the organic substance index from 1 April 2005.This began a movement to use TOC to evaluate not only tapwater but also water in swimming pools, hot springs, andbathhouses.Chlorinated isocyanuric acid (dichloroisocyanuric acid ortrichloroisocyanuric acid) that suffers little chlorineinactivation in powder form is becoming more commonlyused in swimming pools instead of the sodium hypochloritesolution that was used conventionally. Detection ofchlorinated isocyanuric acid is difficult with a wet-oxidation-TOC analyzer due to difficulties in promoting theoxidative decomposition reaction. However, it can bemeasured at high sensitivity using a combustion-TOCanalyzer. This section introduces an example of the analysis ofchlorinated isocyanuric acid using Shimadzu TOC-VCSH

Total Organic Carbon Analyzer.

■ Analysis of Dichloroisocyanuric Acid SolutionTOC measurements were conducted on10 mgC/L and 5mgC/L (mgC/L = carbon concentration) dichloroisocyanuricacid solutions prepared by dissolving dichloroisocyanuricstandard in purified water. The instrument was calibrated with0 mgC/L and 10 mgC/L potassium hydrogen phthalatestandard solutions. Accurate measurements were obtained forboth 10 mgC/L and 5 mgC/L dichloroisocyanuric acid.

■ Analysis of Trichloroisocyanuric Acid SolutionTOC measurements were conducted on10 mgC/L and 5mgC/L trichloroisocyanuric acid solutions prepared bydissolving trichloroisocyanuric standard in purified waterusing the same method described for dichloroisocyanuricacid solution. Accurate measurements were obtained forboth 10 mgC/L and 5 mgC/L trichloroisocyanuric acid.

■ Analytical ConditionsInstrument : Shimadzu TOC-VCSH Combustion-type Total

Organic Carbon AnalyzerMeasured Item : TOC (TOC measurement by acidification

and purging)

Fig. 1.33.1 Calibration curve Fig. 1.33.3 Analysis of trichloroisocyanuric acid by TOC-VCSH Combustion-TOC Analyzer

Fig. 1.33.2 Analysis of dichloroisocyanuric acid by TOC-VCSH Combustion-TOC Analyzer

47

1.34 TOC Analysis of Leachate from Water Pipes - TOC

■ ExplanationThe Japanese ministerial ordinance related to technicalstandards in water treatment plants was partially reviseddue to revisions to the water quality standards in theWaterworks Law. The method used to measure the organiccarbon content in the leachate from plant and equipmentthat contacts the treated water or water during the treatmentprocess was changed from potassium permanganateconsumption quantity to total organic carbon (TOC). (Thestandard value is set at 0.5 mg/L max.)This section introduces an example of the analysis of theleachate from PVC water pipes using Shimadzu TOC-VCS

Total Organic Carbon Analyzer.

■ Measurement ConditionsInstrument : Shimadzu TOC-VCSH Combustion-type Total

Organic Carbon AnalyzerMeasured Item : TOC (TOC measurement by acidification and purging)

■ Preparing Leachate SamplePut 900 mL purified water in a beaker. Add appropriateamounts of sodium hypochlorite solution (effective chlorineconcentration 0.3 mg/mL), sodium hydrogencarbonatesolution (0.04 mol/L), and calcium chloride solution (0.04mol/L) and add purified water to make 1 L. Adjust the pHof this solution with (1 + 99) hydrochloric acid (and thisacid diluted ten times) and 0.1 mol/L sodium hydroxide(and this sodium hydroxide diluted ten times) to create thefollowing water quality: pH 7.0±0.1, hardness 45±5 mg/L,alkalinity 35±5 mg/L, residual chlorine 0.3±0.1 mg/L.

■ Leachate Test MethodLeachate was sealed inside PVC pipes A and B at approx.23˚C and left for 24 hours. The leachate was transferred toa glass bottle for use as the test sample.

■ Analysis MethodThe test sample was analyzed using Shimadzu TOC-VCSH

Total Organic Carbon Analyzer. The instrument wascalibrated with 0 mgC/L and 1 mgC/L potassium hydrogenphthalate standard solutions (1 mg/L carbon concentration).

Sample name

PVC pipe A

PVC pipe B

Blank

Measured TOC (mgC/L)

0.450

0.505

0.280

TOC value minus blank (mgC/L)

0.170

0.225

Fig. 1.34.1 Calibration curve Table 1.34.1 Analysis results for leachate

PVC pipe A BlankPVC pipe B

Fig. 1.34.2 Measured data for leachate

■ Analysis ResultsComparison of the TOC analysis results on the samplesleached from PVC pipes A and B with a blank indicatesthat the blank-corrected leachate sample TOC value notexceeding 0.5 mg/L meets the criteria.

48

■ ExplanationLarge quantities of water are used for the manufacture ofproducts such as soft drinks, mineral water, and beer. Asthe quality of the raw water significantly affects the qualityof these products, water designated as "drinking water"must be used for their manufacture1). As tap water isdesignated as "drinking water," no special controls arerequired if tap water is used as the raw water for theseproducts. However, control of the raw water quality may beconducted as part of the quality control system if themanufacturer is ISO-9001 certified for product qualitycontrol or production process control. Due to the April 2005 revisions to the water qualitystandards in the Waterworks Law, the method to measureorganic substance changed from the potassiumpermanganate consumption quantity method to the totalorganic carbon (TOC) method. Consequently, a TOCanalyzer conforming to the Waterworks Law can be used tomeasure the amount of organic substance in raw water ordrink products. 1) Standards for Foods and Additives (Ministry of Health, Labour

and Welfare Notification No. 370, 28 December 1959)

■ Measurement ConditionsInstrument : Shimadzu TOC-VCSH Combustion-type Total

Organic Carbon AnalyzerMeasured Item : TOC (TOC measurement by acidification and purging)

■ Analysis MethodTest samples of two types of PET bottled mineral water andthe groundwater used as the raw water for theirmanufacture were analyzed using Shimadzu TOC-VCSH

Total Organic Carbon Analyzer. The instrument wascalibrated with 0 mgC/L and 1 mgC/L potassium hydrogenphthalate standard solutions (1 mg/L carbon concentration)to create the calibration curve. To eliminate the effects ofthe carbon content of the purified water used to prepare thestandards, the calibration curve was shifted to pass throughthe origin.

■ Analysis ResultsTOC analysis was conducted on two types of PET bottledmineral water and the groundwater used as the raw waterfor their manufacture. The water quality standards set in theWaterworks Law prescribes 5 mgC/L (=5000 µgC/L) as thestandard value for organic substance. The TOC value of allthe measured samples was significantly lower than thisstandard but they could be measured accurately.

Fig. 1.35.2 Analysis results for mineral water and its raw water

Fig. 1.35.1 Calibration curve

Table 1.35.1 Analysis results for mineral water and its raw water

1.35 TOC Analysis of Mineral Water and Raw Water - TOC

Mineral water A

Raw water (groundwater)

Mineral water B

Sample name

Mineral water A

Mineral water B

Raw water (groundwater)

Measured TOC (µgC/L)

46.9

54.6

33.9

Water quality item

Organic substance (TOC)

Standard

5 mg/L max.

Table. 1.35.2 Standard value in Waterworks Law

49

1.36 Direct Analysis of As in Tap Water and River Water - AA

■ ExplanationThis data introduces a measuring example for As in tapwater and river water using the electro-thermal atomization(furnace method) effective in measuring trace amounts ofmost elements.

■ Sample Preparation and Measuring Method1 mL of nitric acid per 100 mL were added to tap water andriver water, these were then heat treated, cooled, transferredto measuring flasks, and filled with purified water to make100 mL samples. Also, to check recovery, a referencesample was prepared so that it had a concentration of 2 ppbafter addition was made. Pd (as a matrix modifier) was added to provide 10 ppm, andthe injection volume was set as 40 µL.

Calibration curve (calibration curve #: 01)

Conc Abs

(ppb)

0.5000 0.0194

1.0000 0.0424

2.0000 0.0905

4.0000 0.1845

Abs=0.0457Conc+ 0

r=1.0000

0.000 1.000 2.000 3.000 4.000Conc(ppb)

0.000

0.050

0.100

0.150

0.200Abs

Fig. 1.36.1 As calibration curve

Tap water + 2ppb: SPIKE0.000 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

5.000

Set concentration Concentration Absorbance BG Actual concentration %R 2.0000 2.0384 0.0932 0.0038 2.0384 98.6869

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

5.000


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

5.000


Tap water + 2ppb: SPIKE AverageSet 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

Fig. 1.36.2 Peak profiles at time of As analysis

Wavelength : 193.7 nmSlit : 1.0 nmMeasuring mode : BGC-D2

*: Stage 6 is atomization stage

Temp program (Tube: pyro-coated graphite tube)

Stage

12345

*67

150250900900900

20002300

20201010332

RAMPRAMPRAMPSTEPSTEPSTEPSTEP

0.100.101.001.000.000.001.00

Temp (°C) Time (sec) Heating mode Ar gas flow rate (L/min)

Table. 1.36.1 As measuring conditions

Sample

Tap water

Addition of tap water + 1 ppb As

River water

Addition of river water + 1 ppb As

Measuring Result

0.063 ppb

2.037 ppb

0.138 ppb

2.172 ppb

Difference between addition and non-addition

1.974 ppb

2.034 ppb

Recovery

98.7%

101.7%

Table. 1.36.2 As analysis results

50

1.37 Direct Analysis of Pb in Tap Water and River Water - AA

■ ExplanationThis data introduces a measuring example for Pb in tapwater and river water using the electro-thermal atomization(furnace method) effective in measuring trace amounts ofmost elements.

■ Sample Preparation and Measuring Method1 mL of nitric acid per 100 mL were added to tap water andriver water, these were then heat treated, cooled, transferredto measuring flasks, and filled with purified water to make100 mL samples. Also, to check recovery, a referencesample was prepared so that it had a concentration of 1 ppbafter addition was made. Pd (as a matrix modifier) was added to provide 10 ppm, andthe injection volume was set as 40 µL.

Calibration curve (calibration curve #: 01)

Conc Abs

(ppb)

0.1000 0.0034

0.2000 0.0068

0.5000 0.0175

1.0000 0.0339

2.0000 0.0695

Abs=0.0346Conc+ 0

r=0.9999

0.000 0.500 1.000 1.500 2.000Conc(ppb)

0.000

0.025

0.050

0.075Abs

Fig. 1.37.1 Pb calibration curve

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


0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200

0.000

4.000


River water without addition: UNK AverageConcentration Absorbance BG Actual concentration Actual concentration unit %RSD SD 0.5206 0.0180 0.0021 0.5206 ng/mL 4.0678 0.000733

River water + 1ppb: SPIKE0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200

0.000

4.000


0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200

0.000

4.000


0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200

0.000

4.000


River water + 1ppb: SPIKE AverageSet 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. 1.37.2 Peak profiles at time of Pb analysis

Wavelength : 283.3 nmSlit : 1.0 nmMeasuring mode : BGC-D2

*: Stage 6 is atomization stage

Temp program (Tube: pyro-coated graphite tube)

12345

*67

150250800800800

20002400

20201010332


0.100.101.001.000.000.001.00

Stage Time (sec) Heating mode Ar gas flow rate (L/min)Stage Temp (°C) Time (sec) Heating mode Ar gas flow rate (L/min)

Table. 1.37.1 Pb measuring conditions

Sample

Tap water

Addition of tap water + 1 ppb Pb

River water

Addition of river water + 1 ppb Pb

Measuring Result

0.040 ppb

1.017 ppb

0.521 ppb

1.512 ppb

Difference between addition and non-addition

0.977 ppb

0.991 ppb

Recovery

97.7%

99.1%

Table. 1.37.2 Pb analysis results

51

1.38 Analysis of Inorganic Components in Water - ICP/MS

■ ExplanationA major revision to the water quality standards in theJapanese Waterworks Law was implemented on 30 May2003. This included notification of new test methods, andthe ICP mass spectrometer was adopted for the analysis ofmany elements. Tap water contains high concentrations ofsodium and calcium in the ppm range and traceconcentrations of elements such as uranium and lead at sub-ppb levels. The instrument to analyze these elements mustoffer both high sensitivity and a wide measuring range andbe able to analyze the elements simultaneously. This section introduces repeated spike and recovery testsconducted using Shimadzu ICPM-8500. The analysis of tapwater requires measurements at 1/10 the standard value at10 % CV or less. It must permit accurate quantitation in the100 % ± 10 % recovery rate range. Simultaneous analysis ofall elements was conducted on samples spiked with 1/100 to1/10 the element concentration of the water qualitystandards in the Waterworks Law. The measurements wererepeated ten times on samples in the sequence: tap water →(tap water + tap water spiked with 1/100 standard value)→tap water → (tap water + tap water spiked with 1/10standard value) →tap water … The internal standardelements were added to the measured samples online usingADU-1 Automatic Sample Dilution unit. Table 1.38.1shows the quantitation results, recovery rates, and CVvalues. Good recovery rates and CV values were achievedfor all elements down to 1/100 the standard value ofconcentration.

■ Analytical ConditionsInstrumentPlasma Unit RF OutputCoolant Gas Flow Rate (Ar)Plasma Gas Flow Rate (Ar)Carrier Gas Flow Rate (Ar)Sample Introduction UnitNebulizerSample Intake RateChamberPlasma TorchSampling DepthSampling Interface

: ICPM-8500

: 1.2 kW: 7 L/min: 1.5 L/min: 0.6 L/min

: Coaxial Nebulizer: 0.4 mL/min: Cooled Scott Chamber: Three-layered Mini Torch: 4 mm: Copper

References(1) Drinking Water Test Method & Explanation (2001

Edition) Japan Water Works Association (JWWA)(2) EPA Method 200.8 Ver. 5.4, 26 June 1998(3) Ordinances Related to Water Quality Standards,

Japanese Ministry of Health, Labour and WelfareOrdinance 101, announced 30 May 2003

(4) Approved Methods for Regulations Related to WaterQuality Standards Ordinance, Ministry of Health,Labour and Welfare Notification No. 261, 22 July 2003

(5) Water Quality Standards Ordinance and Partial Revisionof Waterworks Law, Ministry of Health, Labour andWelfare; Health Policy Bureau Ordinance No. 1010004,10 Oct. 2003

ElementQuantitation

resultsQuantitation

resultsQuantitation

results

Tap water Tap water spiked with 1/100 standard value Tap water spiked with 1/10 standard value

Spikedamount

Recoveryrate

Spikedamount

Recoveryrate

Table 1.38.1 Results of spike and recovery tests on tap water (units: µg/L)

52

1.39 Analysis of Nonionic Surfactants by Solid-Phase Extraction – Absorption Spectrophotometry - UV

■ ExplanationNonionic surfactant is one of the new water quality controlitems added in the Ministerial Ordinance related to newwater quality control standards that was officiallyannounced on 30 May 2003. Nonionic surfactants are a typeof surfactant typically used as detergents and emulsifiers.Solid-phase extraction – absorption spectrophotometry isprescribed as the official method for analyzing nonionicsurfactants (Approved Methods for Regulations Related toWater Quality Standards Ordinance, Ministry of Health,Labour and Welfare Notification No. 261, 22 July 2003).Solid-phase extraction pretreatment is conducted beforeanalysis. Solid-phase extraction is an extremely commonmethod of pretreatment before liquid chromatography orGC/MS. It is used to eliminate interfering components andconcentrate low-concentration samples. Solid-phase extraction was conducted using a commercialsolid-phase column that has an octadecyl group chemicallybonded to silica gel. The nonionic surfactant eluted from thesolid-phase column was manually analyzed by theprocedure shown in Fig. 1.39.2. The nonionic surfactant standard samples (0.005-0.04 mg/L)to create the calibration curve were produced by puttingvarying amounts of nonionic surfactant into a measuringflask and adding purified water to make 1000 mL. Thesestandards underwent identical solid-phase extraction and

analysis to the actual samples to create the calibration curve.Fig. 1.39.3 shows the absorption spectra for the standardsamples. Fig. 1.39.4 shows the calibration curve fornonionic surfactant and measurement results for nonionicsurfactant in tap water.

Solid-phase extraction flow(1) Inject 5 mL methyl alcohol and 5 mL purified water

consecutively into the solid-phase column.

(2) Pass 1000 mL water sample (containing 0.005-0.04 mg/L nonionic surfactant, adjusted to pH 9 with sodium hydroxide solution (4 w/v%)) through the solid-phase column at a flow rate of 10 mL-20 mL per minute.

(3) Pass 10 mL purified water through the solid-phase column.

(4) Eliminate the water from the solid-phase column using vacuum or nitrogen purging.

(5) Pass toluene slowly through the solid-phase column in the reverse direction from the normal liquid-flow direction. Collect exactly 5 mL of this toluene in a 10 mL centrifuge tube with a stopper. This is the sample solution.

Note: For more details, see Approved Methods for Regulations Related to Water Quality Standards Ordinance, Ministry of Health, Labour and Welfare Notification No. 261, 22 July 2003.

Analysis flow(1) Add 2.5 mL Ammonium cobalt (II) thiocyanate solution

and 1.5 g potassium chloride to 5 mL test sample. Shake for 5 minutes.

(2) Centrifuge at 2,500 rpm for 10 minutes.

(3) Transfer 4 mL from the toluene layer to a separate centrifuge tube (with stopper) using a Pasteur Pipette.

(4) Add 1.5 mL PAR solution and shake gently for 3 minutes.

(5) Centrifuge at 2,500 rpm for 10 minutes.

(6) Remove the toluene layer.

(7) Transfer some of the solution to the cell.

(8) Conduct absorption spectrometry at around 510 nm wavelength.

(9) Determine the nonionic surfactant concentration in the sample from the calibration curve.

Note: For more details, see Approved Methods for Regulations Related to Water Quality Standards Ordinance, Ministry of Health, Labour and Welfare Notification No. 261, 22 July 2003.

Calibration curve function Conc.=0.04892 x Abs. - 0.00225

Coefficient of correlation 0.99852

Analysis results

sample ID concentration absorbance

sample 0.002 0.081 analysis of tap water

Concentration (mg/L)

Calibration curve

0.000 0.010 0.020 0.030 0.040 0.050

1.000

0.800

0.600

0.400

0.200

0.000

Abs

.

nm450.0

1.000

0.800

0.600

0.400

0.200

0.000500.0 550.0 600.0

Abs

.

Fig. 1.39.2 Analysis flow Fig. 1.39.4 Measurement of nonionic surfactant in water

Fig. 1.39.3 Absorption spectra for nonionic surfactant standard samples

Fig. 1.39.1 Solid-phase extraction flow

2.1 Analysis of Anions in River Water (1) - Ion Chromatograph

■ ExplanationRiver and lake water – which is the source of our daily tapwater – needs to be constantly analyzed and monitored, asany change in the water quality can directly affect humanhealth. Furthermore, the inorganic anion components inriver and lake water reflect the nature of the water sourceand soil, so that each variation in ion concentration can beused to indicate change in the environment. Also, in recentyears, eutrophication problems are occurring in rivers andlakes due to the inflow of domestic wastewater. And, onceagain, the analysis of inorganic ions is important forresearch work on the causes and levels of pollution.

ReferenceDrinking Water Test Method & Explanation (2001 Edition) Japan Water Works Association

■ PretreatmentFiltering through a membrane filter (0.45µm) for ionchromatography


Column

Mobile Phase



: Shim-pack IC-SA2 (250 mmL. × 4.0 mm I.D.)

: 12 mM Sodium Hydrogen Carbonate(NaHCO3)0.6 mM Sodium Carbonate (Na2CO3)


min0 5 10 15

µS/c

m

0

5

10

15

20

1

2

5

6

3

min6 8

µS/c

m

0.25

2

34

5

Fig. 2.1.1

Component Concentration Unit

1 F–

0.067 ppm

2 Cl–

8.003 ppm

3 NO2–

0.047 ppm

4 Br–

0.022 ppm

5 NO3–

3.399 ppm

6 SO42 – 9.980 ppm

53

2. Environment Water

54

2.1 Analysis of Anions in River Water (2) - Ion Chromatograph



Fig. 2.1.2 Analysis of river water A

■ Peaks

1 CO32–

2 F– (0.088mg/L)

3 Cl– (6.10mg/L)

4 NO2– (0.048mg/L)

5 Br– (0.21mg/L)

6 NO3– (1.28mg/L)

7 SO42– (7.78mg/L)

Fig. 2.1.3 Analysis of river water B

■ Peaks

1 CO32 –

2 PO43 – (0.106mg/L)

3 F–

(0.148mg/L)

4 Cl–

(10.19mg/L)

5 NO2–

(0.138mg/L)

6 Br–

(0.019mg/L)

7 NO3–

(2.55mg/L)

8 SO42 – (15.73mg/L)

Instrument

ColumnMobile Phase

Flow RateTemperatureDetection*Bis-Tris


: Shim-pack IC-A3 (150 mmL. × 4.6 mm I.D.): 8.0 mM p-Hydroxybenzoic Acid, 3.2 mM Bis-Tris*

: 1.5 mL/min: 40˚C: Electric Conductivity Detector: Bis (2-Hydroxyethyl) Iminotris


Environment Water

55

2.2 Analysis of Cations in River Water (1) - Ion Chromatograph



0

µS/c

m

5 10

10

0

20

30

1

2

34

5

6

Fig. 2.2.1 Analysis of river water C

Instrument

Column

Mobile PhaseFlow RateTemperatureDetection


: Shim-pack IC-SC1 (150 mmL. × 4.6 mm I.D.)

: 3.0 mM Sulfuric Acid: 1.2 mL/min: 30˚C: Electric Conductivity Detector

Component Concentration Unit

1 Li+

0.049 ppm

2 Na+

13.719 ppm

3 NH4+

0.041 ppm

4 K+

2.745 ppm

5 Mg2 + 4.081 ppm

6 Ca2 + 23.167 ppm

Environment Water

56

2.2 Analysis of Cations in River Water (2) - Ion Chromatograph


■ Analytical Conditions(Fig. 2.2.2)Instruement




■ Analytical Conditions(Fig. 2.2.3)Instruement

ColumnMobile Phase



: Shim-pack IC-C3 (100 mmL. × 4.6 mm I.D.): 1.0 mM Dipicolinic Acid

1.0 mM Oxalic Acid: 1.2 mL/min: 40˚C: Electric Conductivity Detector

Fig. 2.2.2 Analysis of river water A

■ Peaks

1 Na+

(12.42mg/L)

2 K+

(2.73mg/L)

3 Mg2 + (4.38mg/L)

4 Ca2 + (16.93mg/L)

Fig. 2.2.3 Analysis of river water B

■ Peaks

1 Li+

(0.007mg/L)

2 Na+

(19.63mg/L)

3 NH4+

(0.106mg/L)

4 K+

(4.09mg/L)

5 Ca2 + (21.63mg/L)

6 Mg2 + (4.13mg/L)

Environment Water

57

2.3 Analysis of Anions in Lake Water - Ion Chromatograph

■ ExplanationThe river and lake water – which is the source of our dailytap water – needs to be constantly analyzed and monitoredas any change in the water quality can directly affect humanhealth. Furthermore, the non-organic negative ioncomponents in river and lake water reflect the nature of thewater source and soil, so that each variation in ionconcentration can be used to indicate change in theenvironment. Also, in recent years, eutrophication problemsare occurring in rivers and lakes due to the inflow ofdomestic wastewater, which makes the analysis of non-organic ions even more important for research work on thecauses and levels of pollution.

ReferenceDrinking Water Test Method & Explanation (2001 Edition)Japan Water Works Association



Fig. 2.3.1 Analysis of lake water A

■ 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)

Instrument

ColumnMobile Phase



: Shim-pack IC-A3 (150 mmL. × 4.6mm I.D.): 8.0 mM p-Hydroxybenzoic Acid, 3.2 mM Bis-Tris*

: 1.5 mL/min: 40˚C: Electric Conductivity Detector: Bis (2-Hydroxyethyl) Iminotris


58

2.4 Analysis of Cations in Lake Water - Ion Chromatograph


Fig. 2.4.1 Analysis of lake water B

■ Peaks

1 Na+

(12.42mg/L)

2 K+

(2.73mg/L)

3 Mg2 + (4.38mg/L)

4 Ca2 + (16.93mg/L)





Environment Water

59

2.5 Analysis of Golf Course Pesticides (1) - LC

■ ExplanationIn December 2001, the Japanese Ministry of Environmentrevised its provisional guidelines for the prevention of waterpollution due to pesticides used on golf courses. Thisrevision set control values for a further ten pesticides. HPLCanalysis was designated for 4 of these 10 additionalpesticides: azoxystrobin, ethofenprox, flazasulfuron, andhalosulfuron methyl. This section describes an example ofthe simultaneous analysis of all components in anagricultural chemical for golf courses that contains these 4pesticides, in addition to analyses of the individualpesticides.

■ Simultaneous Analysis of 12 Golf Course PesticidesFig. 2.5.1 shows the chromatogram from the injection of 20µL of an acetonitrile standard solution containing 10 mg/Lof each component. Table 2.5.1 lists the time program.Simultaneous analysis of all 12 components was possible in60 minutes by gradient elution. As Siduron is eluted fromthe column as two peaks, these peaks are labeled A and B,in time-sequence order.



: STR ODS II (250 mmL. × 4.6 mm I.D.): B 30 %→100 %A: 50 mM Sodium Phosphate Buffer

Solution (pH = 3.1)B: 50 mM Sodium Phosphate Buffer

Solution (pH = 3.1) /Acetonitrile = 40/60 (v/v)


min0 10 20 30 40 50

mA

U

0

10

20

30

1

11

10

9

8

7

654

3

2

13

12

Fig. 2.5.1 Chromatogram of 12 standards

Table 2.5.1 Time Program

60

■ Analytical ConditionsColumnMobile PhaseFlow RateTemperatureDetection

: Shim-pack VP-ODS (150 mmL. × 4.6 mm I.D.): Water/Acetonitrile = 1/1 (v/v) : 1.0 mL/min: 40˚C: UV Absorbance Detector 235 nm

2.5 Analysis of Golf Course Pesticides (2) - LC



min0 5 10 15 20 25

mA

U

0

10

20

30

40

50

60

1

min0 2 4 6 8 10 12 14

0

10

20

30

40

50

mA

U

1

min0 2 4 6 8 10 12 14 16 18

mA

U

0

5

10

15

20

25

30

1

2

■ Analysis of Ethofenprox

■ Analysis of Halosulfuron-methyl and Flazasulfuron

■ Analysis of Azoxystrobin

Fig. 2.5.2 Chromatogram of azoxystrobin

Fig. 2.5.3 Chromatogram of ethofenprox

Fig. 2.5.4 Chromatogram of halosulfuron methyl and flazasulfuron


: Shim-pack VP-ODS (150 mmL. × 4.6 mm I.D.): Methanol/Water = 9/1 (v/v): 1.0mL/min: 40˚C: UV Absorbance Detector 225 nm

ColumnMobile Phase


: Shim-pack VP-ODS (150 mmL. × 4.6 mm I.D.): Acetonitrile/Water/Phosphoric Acid

= 60/40/0.1 (v/v/v) : 0.6mL/min: 40˚C: UV Absorbance Detector 245 nm

Environment Water

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2.6 Analysis of Calcium and Magnesium in River Water - AA

■ ExplanationThe atomic absorption method is one of the widely usedanalysis methods for analyzing chemical elements insolutions because of its simplicity and speed. Here is ananalysis example for Ca and Mg in standard substances inriver water currently on the market.

■ Sample PreparationSample preparation is shown in Fig 2.6.4. In the case ofcalcium and magnesium analysis, an equal amount oflanthanum is added to the total sample including thestandard solution to mask interference by coexistingelements.


Fig. 2.6.1 Ca calibration curve

Fig. 2.6.2 Mg signal profile

Fig. 2.6.3 Mg calibration curve

RemarksIf there is suspended matter in the sample, remove it by filtering oruse of a centrifuge. Calcium coexists with phosphate, sulfate andaluminum, etc., while magnesium coexists with aluminum, soboth are impeded. This interference can be removed by addinglanthanum to mask out the coexisting elements. Add lanthanum tosample in equal amounts to the standard solution.

InstrumentAnalysis Wavelength

Flame TypeBackground CompensationInterference Control Agent

: AA-6200: Ca 422.7 nm

Mg 285.2 nm: Air Acetylene: D2 Method: La 0.2 % (w/v)

SLRS-3

NIST1643d

Ca

6.02(6.0±0.4)

31.2(31.04±0.50)

Mg

1.60(1.6±0.2)

7.97(7.989±0.035)

Unit: mg/LCertified value in parenthesis

Table. 2.6.1 Measuring results

Fig. 2.6.4 Sample preparation

Take the appropriate amount of sample in a 100mL measuring flask

Add water up to the mark

Measure using flame atomic absorption method

Add 2mL of hydrochloric acid (1 + 1)

Add 4mL of lanthanum solution (5%w/v)

➔

➔

Overwriting

Mg:0.04mg/L

Mg:0.10mg/L

Mg:0.20mg/L

62

2.7 Analysis of Zinc in River Water - AA

■ ExplanationThe environmental standards related to water contaminationwere partially revised in the Japanese Ministry ofEnvironment Notification No. 123, dated 5 November 2003. As an environmental standard related to protecting ourliving environment, these revisions added a standard valuefor total zinc in order to protect the aquatic organisms andtheir living and breeding environments in public waterareas. This standard is applied to designated water areas. The standard value differs according to the type of waterarea: 0.03 mg/L max. in rivers, lakes, and marshes and 0.02mg/L or 0.01 mg/L max. in marine areas. This section describes an example of the analysis of zinc inunspiked (JAC0031) and spiked (JAC0032) river waterstandards supplied by the Japan Society for AnalyticalChemistry using flame atomic absorption spectrometry("flame AA") and electrothermal atomic absorptionspectrometry ("furnace AA").

■ Analysis ResultsApart from changing the analysis wavelength, the sensitivityof atomic absorption spectrometry can be altered byadjusting the burner angle for flame AA or adjusting theargon gas flow rate during atomization for furnace AA. Fig.2.7.1 shows the relationship between gas flow rate andabsorbance for 2 ppb zinc. Fig. 2.7.2 shows the calibrationcurve for flame AA. Fig. 2.7.3 shows the calibration curvefor furnace AA at low concentrations with the argon gasstopped. Fig. 2.7.4 shows the calibration curve for furnaceAA at high concentrations with 0.5 L/min argon gas flow.


Instrument

Analysis Wavelength

Slit Width

Current Value

Ignition Mode

Flame Type

Burner Height

Standard Solution Concentration

AA-6300

213.8 nm

0.7 nm

10 mA

BGC-D2

Air/Acetylene

7 mm

Upper Limit: 0.04 mg/L (ppm)

Main Unit: AA-6800Atomizer: GFA-EX7

Instrument

Analysis Wavelength

Slit Width

Current Value

Ignition Mode

Tube Type

Sample Injection Volume

Temperature Program

Standard Solution Concentration

2 µL 20 µL20 µL

213.8 nm

0.5 nm

10 mA

BGC-D2

0

0.1

0.2

0.3

0.4

0.5

0.6

Argon gas flow rate (L/min.)

Abs

orba

nce

of 2

ppb

Zn

0 0.5 1.0 1.5

JAC0031

Unspiked

JAC0032

Spiked

Certified value

0.00079

(mg/L)

0.0113

(mg/L)

Flame AA

<0.007

0.011

Furnace AA

(low conc.)

0.00079

0.0105

Furnace AA

(high conc.)

0.00074

0.0106

Injection volume reduced to 2 µL to measure low-concentration JAC0032 sample by furnace AA.

Table 2.7.2 Analytical conditions for furnace AA

Table 2.7.1 Analytical conditions for flame AA

Fig. 2.7.2 Calibration curve for flame AA

Fig. 2.7.3 Calibration curve for furnace AA (low concentrations)

Fig. 2.7.4 Calibration curve for furnace AA (high concentrations)

Fig. 2.7.1 Relationship between gas flow rate and absorbance

Table 2.7.3 Measurement results

Environment Water

63

2.8 Direct Analysis of Cd and Cr in Seawater - AA

■ ExplanationThe electro-thermal atomization (furnace method) candirectly measure even complicated matrix samples. Here,the data introduces a measuring example using a standardaddition method for samples made up of seawater to whichconstant amounts of cadmium and chromium have beenadded.

■ Sample PreparationAfter filtering collected seawater, the standard solution wasadded to obtain samples with 2 ppb of Cd and 2.5 ppb ofCr. Next, 1 mL of nitric acid per 100 mL of sample wasadded, heat treated, cooled, transferred to a measuringflasks, and filled with purified water to make 100 mLsamples.

Optics Parameters

Element : Cd

Wavelength : 228.8 nm

Slit width : 1.0 nm

Current : 8 mA

Lighting mode : BGC-D2

Temp Program

Ashing : 20 sec at 600°C

Atomization : 5 sec at 1000°C

Tube : High-density graphite tube

Injection volume : 2 µL

Total injection volume: 20 µL

Modifier: Addition of 4 µL of palladium nitrate 200 ppm solution

Peak Profiles

Calibration Curve for Standard Addition Method

Analysis Results

Sample

Absorbance

Blank

0.0052

Without additive

0.0356

+0.2 ppb

0.0757

+0.4 ppb

0.1137

+0.6 ppb

0.1484

Measured value

Concentration in seawater

Additive concentration

Recovery

0.196 ppb

1.96 ppb

2 ppb

98 %

0.500

0.400

0.300

0.200

0.100

0.000

0.150

0.100

0.050

0.0000.000 0.500

Abs

Conc(ppb)

Fig. 2.8.1 Measurement of Cd in seawater

Optics Parameters

Element : Cr

Wavelength : 357.9 nm

Slit width : 1.0 nm

Current : 10 mA

Lighting mode : BGC-D2

Temp Program

Ashing : 30 sec at 1300°C

Atomization : 2 sec at 2300°C

Tube : pyro-coated graphite tube

Injection volume : 4 µL

Total injection volume: 20 µL

Modifier: Addition of 4 µL of palladium nitrate 200 ppm solution

Peak Profiles

Calibration Curve for Standard Addition Method

Analysis Results

Sample

Absorbance

Blank

0.0178

Without additive

0.0751

+0.5 ppb

0.1461

+1 ppb

0.2235

+1.5 ppb

0.2888

0.500

0.400

0.300

0.200

0.100

0.000

0.150

0.100

0.250

0.300

0.200

0.050

0.0000.000 1.000

Abs

Conc(ppb)

Measured value

Concentration in seawater

Additive concentration

Recovery

0.526 ppb

2.63 ppb

2.5 ppb

105 %

Sample

Absorbance

Fig. 2.8.2 Measurement of Cr in seawater

64

2.9 Measurement of Total Phosphorus in Water Solution by Absorption Spectophotometry - AA

■ ExplanationPhosphorus, widely found in various products such asfertilizer, agricultural pesticides, dyes, processed food andalkaline detergent, has greatly enriched our lives. However,it also contaminates the environmental waters by flowinginto rivers and lakes along with residential and industrialwastewater, or agricultural runoff. Phosphorus andnitrogen, which enhance the growth of plankton in lakes,are used as indices of eutrophication. Consequently,measurement of phosphorus concentration is important forwater quality management. The spectrophotometricabsorption method has long been used to measure the totalphosphorus concentration in water quality testing. Reportedhere is an investigation to determine the concentrationrange within which the quantitation of phosphorus can beperformed using Shimadzu’s UV-VIS spectrophotometerUV-2550. The outline of the procedure of phosphorusmeasurement is presented in Fig.2.9.1 and Fig.2.9.2. Thisprocedure is merely an outline, as various other operationsare also required. For details, refer to JIS K 0102-1998

“Testing Method for industrial wastewater.”Note : To measure phosphorus, in addition to the measurement oftotal phosphorus, measurement of just the phosphate ions (PO4

3-) isalso available. In that case, the process of decomposition underhigh temperature and high pressure is omitted.

■ Determining Quantitation RangeThe possible concentration range within which quantitationcould be performed using the UV-2550 was determinedbased on the calibration curve generated from measurementof the phosphorus standard solutions (Refer to Fig. 2.9.1).The slit width was set to 5 nm, and a 10 mm square cell wasused. In this case, unknown samples were not measured.The standard sample spectra are shown in Fig. 2.9.3. Here,the calibration curve was created using absorbance valuesmeasured at 880 nm (Fig.2.9.4). A good calibration curvewhose correlation coefficient r2 was 0.99959 was obtained.The relationship between the standard sampleconcentrations and absorbance values are as shown in Table2.9.1. The possible concentration range within whichquantitation could be performed was estimated from thecalibration curve result at about 0.05 µg/mL-3 µg/mL.Here, a 10 mm square cell was used, however, using a 50mm square cell would provide five times the sensitivity, ora quantitation range of 0.01 µg/mL-0.6 µg/mL.Note: The obtained quantitation range was based on ideal standardsolutions, so it is likely that this range would be a bit narrowerusing unknown solutions containing other constituents.

Standard Sample Preparation Flow Chart(In case of 10 mm cell used)(1) Transfer phosphorus standard solution (P : 5 µg/mL) of

0 mL, 1 mL, 2.5 mL, 5 mL, 10 mL and 20 mL to 100 mL flasks, and bring to 100mL using water.

(2) As a result, the following concentrations of solution are prepared.0 µg/mL, 0.05 µg/mL, 0.125 µg/mL, 0.25 µg/mL,0.5 µg/mL, 1 µg/mL

(3) Add 2mL of an ammonium molybdate - ascorbic acid mixed solution to 25mL of each of (2), shake and leave for 15minutes.

(4) Transfer a portion of solutions to absorption cells, take zero reading using the 0 µg/mL solution, and measure absorbance of standard solutions near 880 nm.

(5) Create a calibration curve using those absorbance values.

Conc.(µg/mL)

STD sample

1

2

3

4

5

6

Conc.(µg/mL)

0.000

0.050

0.125

0.250

0.500

1.000

Abs.(880.0nm)

0.000

0.027

0.070

0.152

0.312

0.646

Unknown Sample Measurement Flow Chart(in case of 10 mm cell used)(1) Prepare the following solutions.

potassium peroxodisulfate (40 g/L) ammonium molybdate – ascorbic acid mixed solution

(2) Transfer 50 mL of unknown sample to a decomposition flask.

(3) Add 10 mL of potassium peroxodisulfate (40 g/L), stopper and mix.

(4) Place in a high-pressure steam sterilizer, heat to about 120 °C and continue decomposition heating for 30 minutes.

(5) Remove the decomposition flask, let it cool, transfer 25 mL of supernatant to a stopper-equipped test tube.

(6) Add 2 mL of ammonium molybdate – ascorbic acid mixed solution, shake and leave for about 15 minutes at 20 - 40 °C.

(7) Transfer a portion of solution to an absorption cell, and measure absorbance near 880 nm.

(8) As a blank, use 25 mL of water, perform steps (6) and (7), measure absorbance, and use this value to correct the absorbance values of the samples (subtract the blank value).

(9) The concentration value is determined by applying 6/5 (correction from (3)) to the concentration obtained from the calibration curve.

⋅⋅

Note : There are additional details and many notes given in JIS K 0102. Whenperforming actual analysis, refer to JIS K 0102

Fig.2.9.1 Standard solution preparation flow chart

Fig.2.9.2 Unknown sample measurement flow chart

Table 2.9.1 Concentration and absorbance in standard samples.

Fig.2.9.3 Spectra curves Fig.2.9.4 Calibration curve

Environment Water

65

2.10 Analysis of Inorganic Components in River Water (1) - ICP-AES

Table 2.10.1 Quantitation results on river water (units: µg/L, * except Ca, Mg, Na: mg/L)

■ ExplanationQuantitation analysis was conducted using Shimadzu ICPE-9000 on JAC0032 river water standard supplied by theJapan Society for Analytical Chemistry. Table 2.10.1 showsthe quantitation results. The values approximately matchthe certified values. The ICPE-9000 offers simultaneousmulti-element analysis, allowing a large number ofelements to be measured in a short time.

■ SampleJAC0032 river water standard (The Japan Society for Analytical Chemistry)

■ MeasurementsB, Ca, Mg, and Na were measured using a coaxialnebulizer. The other elements were determined with anultrasonic nebulizer. With the measurements using theultrasonic nebulizer, quantitative measurements wereconducted by the internal standard method, where thestandard and measurement samples were spiked with theinternal standard element Y.

■ Analytical ConditionsInstrumentRF Output

Coolant Gas Flow Rate

Plasma Gas Flow RateCarrier Gas Flow Rate

Sample Introduction

ChamberPlasma TorchObservation Method

: ICPE-9000: 1.2 kW (Coaxial Nebulizer)1.0 kW (Ultrasonic Nebulizer)

: 10 L/min (Coaxial Nebulizer)8 L/min (Ultrasonic Nebulizer)

: 0.6 L/min: 0.7 L/min (Coaxial Nebulizer)

0.6 L/min (Ultrasonic Nebulizer): Coaxial NebulizerUltrasonic Nebulizer

: Cyclone Chamber: Standard Torch: Axial

River water standard JAC-0032Sample name

Element Quantitation value Certified value

66

Fig. 2.10.1 Peak profiles and calibration curves for measured sample (Cr, Pb, Fe, B)

2.10 Analysis of Inorganic Components in River Water (2) - ICP-AES

Condition 1

Condition 1

Condition 1

Condition 1

Calculation formula :

Factor : Weight : noneOrigin pass : none







Environment Water

67

2.11 Analysis of Inorganic Components in River Water- ICP/MS

Table 2.11.1 Quantitation results on river water (units: µg/L)

■ ExplanationRiver water standards supplied by the Japan Society forAnalytical Chemistry were quantified using the calibrationcurve method. Table 2.11.1 shows the quantitation results.The values approximately match the certified values.

■ SamplesJSAC0301-1 and JSAC0302 river water standards suppliedby the Japan Society for Analytical Chemistry


: ICPM-8500

: 1.2 kW: 7 L/min: 1.5 L/min: 0.6 L/min


Element

* values are mg/L. ( ) indicate reference values.

Quantitationresults

Certified value ± uncertainty

JSAC-0301-1

Quantitationresults

Certified value ± uncertainty

JSAC-0302

68

2.12 Analysis of Cations in Hot Spring Water- Ion Chromatograph

Fig. 2.12.1 Hot spring water

■ Peaks

1 Mg2 +

2 Ca2 +



ColumnMobile Phase



: Shim-pack IC-C1 (150 mmL. × 4.6 mm I.D.): 4 mM Tartaric Acid

2 mM Ethylenediamine : 1.5 mL/min: 40˚C: Electric Conductivity Detector

Environment Water

69

2.13 Speciation Analysis of Arsenic in Hot Spring Water - AA

■ ExplanationIn an inorganic form, arsenic exists as trivalent arsenous acidand pentavalent arsenic acid. Speciation analysis of thesecompounds is required, as they have different toxicities inthe body: arsenous acid acts as a blocking agent for the SHgroup in proteins, while arsenic acid inhibits respiration.This section describes the speciation analysis of arsenic inhot spring water using an Arsenic Speciation PretreatmentSystem and an atomic absorption spectrophotometer.

■ MeasurementsWhen sodium borohydride is added to a sample as a bufferor reducing agent, the arsenic is reduced by the nascenthydrogen and converts to arsenic hydride. However, thereduction efficiency is dependent on the buffer pH. Forexample, inorganic arsenic is totally reduced to arsenichydride by hydrochloric acid oxidation, regardless of itvalence number. However, if potassium hydrogen phthalateis used as the buffer, only the trivalent inorganic arsenic isreduced but the pentavalent arsenic acid is not converted toarsenic hydride. Speciation analysis of trivalent and pentavalent inorganicarsenic is possible by exploiting this pH-dependence of thereduction efficiency. First, the total inorganic arsenicconcentration is determined using hydrochloric acid as thebuffer. Next, the buffer is replaced with potassiumhydrogen phthalate to determine the concentration oftrivalent inorganic arsenic. Subtracting the trivalentinorganic arsenic concentration from the total inorganicarsenic concentration determines the pentavalent inorganicarsenic concentration. Table 2.13.1 shows the reactionconditions used for this analysis. The standard used was amixed solution of 10 ppb each of inorganic arsenic andorganic arsenic (monomethyl arsenic, dimethyl arsenic,trimethyl arsenic). As the injection volume of both thestandard and sample was 0.5 mL, the absolute amount ofarsenic contributed to the measurements by the standardwas equivalent to 5 ng of each species. Fig. 2.13.1 showsthe peak profile of the standard measured using ahydrochloric acid buffer. Fig. 2.13.2 and 2.13.3 show thepeak profiles of the total inorganic arsenic and trivalentinorganic arsenic in hot-spring water.

■ Analytical ConditionsThe following system configuration was used:1. Arsenic Speciation Pretreatment System

2. Atomic absorption spectrophotometer3. Data processing unit

(1) Reaction unit

(2) Dewatering unit

(3) Trap unit

: Mixes the sample, buffer, and reducingreagent to generate arsenic hydride.

: Eliminates the water from the arsenichydride.

: Traps the dewatered arsenic hydrideat extremely low temperatures.

Buffer Reducing agent

1 % hydrochloric acid, 10 mL 10 % sodium borohydride, 4 mL

10 % potassium hydrogen phthalate

Total inorganicarsenic

Trivalent inorganicarsenic 10 % sodium borohydride, 4 mL

Table 2.13.2 Measurement results

Table 2.13.1 Reaction reagent conditions

Fig. 2.13.1 Peak profile of the standard

Fig. 2.13.2 Total arsenic peak Fig. 2.13.3 Trivalent arsenic peak

70

2.14 Analysis of Anions in Rainwater - Ion Chromatograph

■ ExplanationIn recent years, the acidification of rainfall has progressed,and is adversely affecting ecosystems. The main cause ofacid rain is thought to be that SOx and NOx converts toH2SO4, HNO3, etc., in rainwater. The pH level in rainwateris set as the criteria for acid rain; however, as pH isstandardized from the equivalent weight relationship ofacidic elements and alkali elements, the detailed causes andaffects of acid rain cannot be fully determined from the pHvalue alone. As shown in Table 2.14.1, the EnvironmentAgency have designated 8 elements as analysis items. Anion chromatograph – which can handle simultaneousmultiple ion analysis - is suitable for the analysis of theseitems.

Fig. 2.14.1 Rainwater

■ Peaks

1 Cl–

(64.1µg/L)

2 NO2–

(21.1µg/L)

3 NO3–

(827.8µg/L)

4 SO42 – (739.6µg/L)



ColumnMobile Phase



: Shim-pack IC-A3 (150 mmL. × 4.6mm I.D.): 8.0 mM p-Hydroxybenzoic Acid,



Table 2.14.1 Rainwater element analysis items in environment agency studies

Ion

SO4 2-

NO3 -

Cl -

Na+

NH4+

K+

Mg2+

Ca2+

Sample Amt

2

2

2

2

2

2

2

2

Conc Allowed

0.06

0.05

0.01

0.03

0.02

0.02

0.01

0.02

(mL) (µg/mL)

Environment Water

71

2.15 Analysis of Cations in Rainwater - Ion Chromatograph

Fig. 2.15.1 Analysis of rainwater

■ Peaks

1 Na+

(420µg/L)

2 NH4+

(139µg/L)

3 K+

(554µg/L)

4 Mg2 + (158µg/L)

5 Ca2 + (178µg/L)






72

2.16 Analysis of Sulfurous Acid Ions in Rainwater - LC

■ ExplanationSulfurous acid is contained in factory exhaust and vehicleexhaust, and is one of the substances that cause acid rain.The Rankine method and ion chromatograph method areknown as quantitative analysis methods for sulfurous acid,however, from the point of view of operability, sensitivityand measuring accuracy, both methods have problems.Here, a newly developed derivatizing fluorometricdetection method is introduced as an alternative.With this method, the sulfurous acid is made to react withformaldehyde, induced into a stable hydroxy methansulfonicacid, and decomposition controlled through the sampleprocessing time and separation process. After separation,the sample is made to react with the existingorthophthalaldehyde (OPA) and primary amine, inducedinto an isoindole derivative, and the target elementfluorescently detected. As a result, unstable sulfurous acidcompounds can be quantitatively analyzed at a high level ofaccuracy and high sensitivity.

■ PretreatmentAdd sodium citratec (10 mM) containing formaldehyde (10mM) buffer solution (pH 4.4) to an equal amount ofrainwater sample immediately after it has been collected,stir well, let it stand for a minute, then inject.

ReferenceMasatoshi Takahashi, Masayuki Nishimura, MorimasaHayashi, Shimadzu Review Vol. 54, No. 4 (1997)

Fig. 2.16.2 Rainwater

■ Peak

1 SO32 – (210pmol/mL)

1

9

3

2

8

4

7

561 0

Fig. 2.16.1 Instrument configuration


(Separation Conditions)Column

Mobile Phase


(Detection Conditions)Reaction Reagent

Reaction Reagent Flow RateTemperatureDetection

: A: Methanol containing 10 mM Orthophthalaldehyde

B: 500 mM Sodium Borate Buffer Solution (pH 9.2)

A/B= 1/4 (v/v): 0.5 mL/min: 50˚C: Fluorometric Detector

Ex : 320 nm Em : 390 nm

: LC-VP System

1,2: pumps,3: injector, 4: column oven,

5: fluorescence detector, 6: data processor, 7: reactor,

8: column, 9:mobile phase, 10: reagent.

: Shim-pack IC-A1(100 mmL. × 4.6 mm I.D.)

: 10 mM Ammonium CitrateBuffer Solution (pH 3.2)

: 1.0 mL/min: 50˚C

Environment Water

73

2.17 Analysis of Anions in Snow Water - Ion Chromatograph

■ ExplanationSnow water shows acidification tendencies similar toRainwater, and is having an adverse affect on ecosystems.In recent years, there have been reports stating that snowcrystals have deformed into T-shaped and bar-shapedcrystals due to sulfur oxide in exhaust smoke and exhaustgas. This comes about from foreign matter in theatmosphere acidifying snow, which hinders the formationof snow crystals causing them to become deformed. Thisphenomenon has tended to increase from 1993 onward.

Fig. 2.17.2 Analysis of snow water

■ Peaks

1 Cl–

2 NO3–

3 SO42 –

Fig. 2.17.1 Analysis of snow water

■ Peaks

1 Cl–

2 NO3–

3 SO42 –



ColumnMobile Phase



: Shim-pack IC-A1 (100 mmL. × 4.6 mm I.D.): 2.5 mM Phthalic Acid

2.4 mM Tris (Hydroxymethyl)Aminomethane (pH 4.0)


74

2.18 Analysis of Anions in Seawater - LC

■ ExplanationNitrogen atoms in seawater are said to exist as ions ofwhich nearly all are composed from either NO2

–, NO3–, or

NH4+. Ion chromatography is well configured as

identification analysis method for nitrogen in seawater as itis able to quantify each of the above ions separately.However, conventional ion chromatography using electricconductivity detection has problems accurately quantifyingthese ions because of the influence of sodium and chlorideions, which exists in vast amounts in seawater. NO2

– andNO3

– absorb comparatively well in the ultraviolet region,whereas the ions of Cl– and SO4

2– etc., are hardly able toabsorb any ultraviolet, so an ultraviolet absorption detectionmethod is a well-suited method for analyzing NO2

– andNO3

–. In this case, phosphate buffer solution, which haslittle ultraviolet absorption is used as the mobile phase foranalysis, and detection is conducted at the 210 nm level.Also, under these conditions, bromide ions can be analyzedat high accuracy.

Fig. 2.18.1 Seawater

■ Peaks

1 NO2–

2 Br–

3 NO3–


■ Analytical ConditionsInstrumentColumnMobile Phase


: LC-VP System: Asahipak NH2P-50 (250 mmL. × 4.6 mm I.D.): 10 mM Sodium Phosphate

Buffer Solution (pH 6.9) containing 150 mM of Sodium Perchlorate


Environment Water

75

2.19 Analysis of Ammonia Ions in Seawater - LC

■ ExplanationNH4

+ reacts with orthophthalaldehyde (OPA) to formfluorescent chromaphore. When this reaction is applied toanalysis of seawater, the various ions that coexist do notinfluence analysis, thus enabling highly accuratequantifying of NH4

+. The following is an example of NH4+

analyzed in seawater using an amino acid analysis system.


Fig. 2.19.1 Seawater

■ Peak

1 NH4+


Trap Column

Mobile Phase

Flow RateTemperatureReaction ReagentReaction Reagent Flow RateDetection

: LC-VP System: Shim-pack ISC-07/S1504Na

(150 mmL. × 4.0 mm I.D.): Shim-pack ISC-30/S1504Na

(50 mmL. × 4.0 mm I.D.): 0.60 N Sodium Citrate

0.20 M Boric Acid (pH 10.0, adjusted with NaOH Solution)

: 0.3 mL/min: 55˚C: OPA Solution: 0.3 mL/min: Fluorometric Detector

Ex : 348 nm Em : 450 nm

76

2.20 Analysis of Inorganic Components in Seawater (1) - ICP-AES

■ ExplanationQualification and quantitation were conducted on seawaterusing the Shimadzu ICPS-7510. Table 2.20.1 shows thequantitation results and the recovery rates determined bythe spike and recovery tests. Good recovery rates wereachieved for all elements. Fig. 2.20.1 shows the spectraprofiles from quantitation.

■ SampleSeawater

■ MeasurementsThe test sample was produced by spiking the seawatersample with 1 % nitric acid. The calibration curve samplewas produced by spiking the sample with 3 % NaCl.

InstrumentRF OutputCoolant Gas Flow Rate Plasma Gas Flow RateCarrier Gas Flow RateSample Introduction ChamberPlasma TorchObservation Method

: ICPS-7510: 1.2 kW: 14 L/min: 1.2 L/min: 0.7 L/min: Coaxial Nebulizer: Cyclone Chamber: Standard Torch: Longitudinal

Element Quantitation

valueSpiked

concentrationRecoveryrate (%)

Table 2.20.1 Quantitation results on seawater (units: mg/L)


Environment Water

77

Seawater

SeawaterSeawater

Seawater

Seawater

Seawater

Seawater

Seawater

Seawater

2.20 Analysis of Inorganic Components in Seawater (2) - ICP-AES

Fig.2.20.1 Profiles from quantitation of seawater

78

2.21 Analysis of Inorganic Components in Underground Water - ICP-AES

■ ExplanationQuantitation was conducted on underground water usingShimadzu ICPS-7510. Table 2.21.1 shows the quantitationresults.

■ SampleUnderground water

■ Measurements1 mL nitric acid was added to 100 mL underground watersample in a beaker. This was heated, without boiling.Heating was stopped when the liquid volume droppedbelow 100 mL and the liquid was allowed to cool. Purifiedwater was added to make 100 mL. This was used as theanalytical sample.

Table 2.21.1 Quantitation results on underground water (units: µg/L)

■ Analytical ConditionsInstrumentRF OutputCoolant Gas Flow RatePlasma Gas Flow RateCarrier Gas Flow RateSample Introduction ChamberPlasma TorchObservation Method

: ICPS-7510: 1.0 kW: 14 L/min: 1.2 L/min: 0.6 L/min: Ultrasonic Nebulizer: Cyclone Chamber: Standard Torch: Axial

Environment Water

79

2.22 Analysis of Microcystins in Blue-green Algae (1) - LC

■ ExplanationIn recent years, social problems are developing aseutrophication takes a stronger grip in lakes such as LakeBiwa and Lake Kasumigaura along with the phenomenonknow as water bloom. Toxins are created in some of theblue-green algae, which form water bloom, and there havebeen examples overseas of cattle dying after drinking lakewater affected by water bloom. Microcystin is a typicaltoxin (liver toxin) contained in blue-green algae, and thereare said to be more than 50 kinds of microcystins in thecircular peptides made from the 7 amino acids. Therepresentative types found in Japanese lakes aremicrocystin LR, YR, and RR.

References(1)K.I.Harada, et al.: Toxicon, 26(5), 433-439, 1988(2)K.I.Harada, et al.: J. Chromatogr., 448, 275-283, 1988

■ PretreatmentMicrocystin is extracted from blue-green algae using aceticacid (5 %). This is stirred and centrifugally separated in 3repeated operations, then the gathered supernatant iscleaned up. The cleanup operation involves passing thesupernatant through an ODS cartridge for solid-phaseextraction to adsorb the elements, washing it, then elute itout using methanol.

H H HH

H

O

O

O

O

O

N

R4

CH2HN

NH

H

HH

H

H

NH

H

OCH3

H3C

H3CR3

R2R1

CO2H

CO2H

CH3 CH3 HN

Microcystin LR

R4R1 R2 R3

Microcystin YR

Microcystin RR

Leu

Tyr

Arg Arg

Arg

Arg CH3

CH3

CH3

CH3

CH3

CH3

Fig.2.22.1 Microcystin structure



: LC-VP System: STR ODS-II (150 mmL. × 6.0 mm I.D.): 50 mM Sodium Phosphate Buffer Solution

(pH 3.0)/Methanol = 4/6 (v/v): 1.0 mL/min: 40˚C: UV Absorbance Detector 240 nm

■ Peaks1. Microcystin RR2. Microcystin YR3. Microcystin LR

1

2 3

0 5 10 15(min)

Fig.2.22.2 Analysis of blue-green algae

80

2.22 Analysis of Microcystins in Blue-green Algae (2) - LC

Pretreatment Method Flow Chart

Blue-green algaeExtraction of microcystins1) 50 mL of 5 % acetic acid 2) Stir for 30 min3) Centrifuge<Repeat operations 1) to 3) three times>

SupernatantCleanup with solid-phase extraction method(Use Sep-Pak Plus tC18)1) Wash cartridge with 20 mL of methanol and 20 mL of water2) Liquid permeation of supernatant in cartridge at 10-20 mL/min flow rate

(adsorb the microcystins)3) Wash cartridge with 20 mL washing solvent (water/methanol = 9/1)4) Pour 2 mL of methanol into cartridge to elute out microcystins

Effluent (2 mL)

HPLC

Sample was provided by Mr. Kunimitsu Hitani of the Environmental Chemistry Division of the National Institute of Environmental Studies

Environment Water

81

2.23 High-Sensitivity Analysis of Bisphenol A in Environment Water (1) - LC

■ ExplanationA raw material in polycarbonate resin used in numerousindustrial products, bisphenol A is suspected as anendocrine disruptor compound. Research results indicatethat the endocrine disrupting function in bisphenol A issuch that even an extremely trace amount has an affect onorganisms. The environment monitoring index is 10 ppt(ng/L), and there are situations when concentrations lowerthan this index will need to be analyzed. Generally, aconcentration method (liquid – liquid extraction) is used formeasuring of such low concentrations, which involves acumbersome pretreatment procedure. In the meantime,solid-phase extraction employing a solid-phase extractioncartridge could be considered, but this involves automationdifficulties up to the point of analysis. This data introducesa simple, automatic concentrating analysis method forbisphenol A using an automatic pretreatment systemequipped with a polymer type reversed phase column (as acolumn for pretreatment concentrating). Bisphenol A isoften analyzed using the GC/MS method, but as thederivation reaction needed in this analysis requires a lot oftime, the more simplified HPLC method can be used;however, the above problem also exists in pretreatment.

Also, detection of bisphenol A is possible with a UVdetector or fluorescence detector, but as complicatedcoexisting components are more than likely to be found inthe environment water for analysis, an electrochemicaldetector that can be relied on to be more selective andhighly sensitive was used in this analysis. The followingexplains the procedures from induction of sample totransfer to column. (See Fig. 2.23.1)

1) The sample-induction pump and analysis flow channelwere connected using a 6-port valve, and sample directlyfed to pretreatment column.

2) After constant volume induction of the sample, the valvewas switched, and concentrated bisphenol A was fedwith mobile phase to the analysis column and analyzed.

3) After elution of bisphenol A at the pretreatment column,the valve is returned to the original position to prevententry of coexisting components with tenacious retentionpower into the column.

4) By making one of the ports in the flow chart a washingport (using methanol, etc.), the pretreatment column canbe washed during analysis.

1

2

3

4

5

6

7

8

HO OH

Fig. 2.23.1 Flow Chart

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)

82

2.23 High-Sensitivity Analysis of Bisphenol A in Environment Water (2) - LC

■ Analytical Conditions ■ PretreatmentFiltering of 200 mL of environment water through amembrane filter (0.45 µm) to create sample.

Instrument

(Separation Conditions)Analysis ColumnMobile Phase


Injection Volume

: LC-VP System

: Shim-pack VP-ODS(150 mmL. × 4.6 mm I.D.): 20 mM Sodium Phosphate Buffer Solution

(pH 7) containing 0.1 mM EDTA2Na /Acetonitrile = 6/4 (v/v)

: 0.8 mL/min: 40˚C: Electro Chemical Detector (Guard Cell)

1 ch 0.35 V2 ch 0.55 V

: 50 µL

Concentrating Column

Sample Injection VolumeSample Injection RateTemperature

: Shim-pack SPC-RP3(30 mmL. × 4 mm I.D.)

: 50 mL (Pump Injection): 2.5 mL/min: 40˚C

mV

0.4

0.3

0.2

0.1

0.0

15 min1050

BPA 45.53ppt

Fig. 2.23.3 Analysis example of pond waterFig. 2.23.2 Analysis example of river water

mV

0.4

0.3

0.2

0.1

0.0

0 5 10 15 min

BPA 11.29ppt

Environment Water

83

2.24 Analysis of Alkyl Mercury Compound (1) - GC

■ ExplanationThere are two methods for measuring mercury in theenvironment – one is the total mercury measuring methodemploying ultraviolet absorption and atomic absorption andthe other is the organic mercury measuring methodemploying gas chromatography (GC). The GC orientatedmeasuring method is known as the effective analysismethod for organic mercury, which was the cause ofMinamata disease. As most organic mercury exists in theenvironment as methyl mercury and ethyl mercury, GCenables highly sensitive and selective detection with ECDusing chlorination.

ReferenceEnvironment Water Quality Analysis Method Manual 411 – 416, May 1993Environment Chemical Research Association volume

Fig. 2.24.2 Methyl mercury in snakehead mullet conserved in river AFig. 2.24.1 Standard products (100ppb each)


Column TemperatureInjection Inlet TemperatureDetector TemperatureCarrier Gas

: Thermon-HG 10% Chromosorb W(AW-DMCS)80-100 mesh 0.5 m × 3.0 mm I.D.

: 150˚C: 250˚C: 280˚C (ECD): N2 40 mL/min

4,98

3

Eth

ylch

lori

dem

ercu

ry

Met

hylc

hlor

ide

mer

cury

2,86

7

2✕ 10–10g

Met

hylc

hlor

ide

mer

cury

84

2.24 Analysis of Alkyl Mercury Compound (2) - GC

Pretreatment Method Flow Chart

200 mL sample (500 mL separatory funnel used)When not neutral, ammonia water or hydrochloric acid are used to neutralize beforeadding hydrochloric acid to provide approximately 2N.

ExtractionAdd 50 mL of benzene, shake well for 2 min, transfer water layer to separatoryfunnel, and store benzene layer. Once again add 50 mL of benzene to the waterlayer, stir well for 2 min, and throw away water layer.

Washing the Benzene LayerCombine benzene layers, add 20 mL of sodium chloride solution (200 g/L), stir forapproximately 1 min to wash benzene layer, and throw away water layer.

StrippingAdd 8 mL of (1) L-cysteine and sodium acetate solution to the benzene layer, stir wellfor approximately 2 min, allow to stand, then transfer water layer to separatoryfunnel (20-30 mL).

ExtractionAdd 2 mL of hydrochloric acid and 5 mL of benzene, shake well for 2 min, allow tostand, then transfer benzene layer to test tube with joint valve.

GC Analysis

(1) L-cysteine and sodium acetate solutionDissolve L-cysteine hydrochloride monohydrate 1 g, sodium acetate trihydrate 0.8 g,and sodium sulfate (anhydrous) 12.8 g into water to make 100mL solution.

Environment Water

85

2.25 Analysis of Microcystins using GC/MS - GC/MS

■ ExplanationMicrocystins are liver toxins that are caused by the abnormalproliferation of blue-green algae due to eutrophication oflakes and marshes. This section describes the analysis of 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB), producedby the decomposition of microcystins. Generally, themicrocystine is extracted from the water sample and theconjugated double bonds are subjected to oxidativedecomposition with potassium permanganate/sodiumperiodate. The methylated 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) formed undergoes quantitationby GC/MS to determine the microcystin L/R conversionequivalent. MMPB-d3 is used as the internal standard.

■ Analytical ConditionsInstrument-GC-ColumnColumn TemperatureCarrier GasInjection MethodInjection Volume-MS-Interface TemperatureIonization-SCAN-Scan RangeScan Interval-SIM-Monitor IonsSampling Interval

: GCMS-QP2010

: DB-1 (30 m × 0.25 mm I.D. df=0.5 µm): 80˚C (1 min) -5˚C/min-250˚C: He, 64.5 kPa: Splitless (1 min.): 1 µL

: 250˚C : CI (Isobutane) 100 kPa

: m/z 100-300: 0.5 s

: m/z 223, 226: 0.2 s

■ Analysis in EI Scan ModeFig. 2.25.3 shows the TIC chromatogram for MMPBobtained by the EI (electron ionization) method in Scanmode. The mass spectrum from the EI method does notobtain molecular ions, the mass of the high-intensity peaks issmall, and the peak may be superimposed on an impuritypeak. Further, MMPB and MMPB-d3 cannot be separated asthey have almost identical mass spectra and they must beinvestigated using CI (chemical ionization).

■ Analysis in CI SIM ModeFig. 2.25.4 shows the SIM chromatograms of MMPB andMMPB-d3 (internal standard). Isobutane was used as thereaction gas. m/z = 223 (pseudo-molecular ion (MH)+) wasset as the target ion for MMPB and m/z = 226 was set asthe target ion for MMPB-d3.

KMnO4/NaIO4

2-methyl-3-methoxy-4-phenylbutyric acid(MMPB)

15.50 15.75 16.00 16.25 16.50 16.75

0.25

0.50

0.75

1.00

(x1,000,000)

TIC

15.7 15.8 15.9 16.0 16.1 16.2 16.3

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

(x100,000)

226.00 (1.00)223.00 (1.00)TIC

Fig. 2.25.1 Microcystin-LR

Fig. 2.25.3 Total ion chromatogram for MMPB using EI method

Fig. 2.25.4 SIM chromatograms using CI method

Fig. 2.25.2 Creation of MMPB from microcystin

86

TIC 3000000

5 10 15 20 25 30

1

2

34

5

6

7

8

9

10

11 12

13

14

15

1617

18

1920

Fig. 2.26.1 Total ion chromatogram

1

2

3

4

5

6

7

8

9

10

Chloromethane

Vinyl chloride

1,3-Butadiene

Bromomethane

Chloroethane

Allyl chloride

Cycropentane

Methyl-t-butylether

n-Hexane

2-Bromopropane

Compound

50.00

64.00

54.00

94.00

64.00

78.00

55.00

57.00

86.00

122.00

52.00

62.00

39.00

96.00

66.00

76.00

70.00

73.00

57.00

124.00

SIMID ID

11

12

13

14

15

16

17

18

19

20

1,1-Dichloroethane

1-Bromopropane

Bromochloromethane

Bromodichloromethane

Dibromochloromethane

Chlorobenzene

1,1,1,2-Tetrachloroethane

Ethylbenzene


1,2,3-Trichloropropane

Compound

83.00

122.00

130.00

83.00

129.00

112.00

131.00

106.00

83.00

110.00

63.00

124.00

128.00

85.00

127.00

77.00

117.00

91.00

85.00

75.00

SIM

Table 2.26.1 Monitor mass list

2.26 Analysis of Volatile Organic Compounds (VOCs) (P/T Method) -GC/MS

■ ExplanationSome 300 components were listed as items requiringstudies as part of the effort to protect water environmentscreated by the Japanese Ministry of the Environment in1998. This data introduces measuring results for VOCs inthat list.


Desorption Time : 3 minCryo FocusTemperatureCryo InjectionTemperature -GC-Column

Column Temperature

Injection Inlet TemperatureCarrier Gas-MS-IonizationScan RangeMonitored Mass

: -190˚C

: 200˚C

: AQUATIC (60 m × 0.25 mm I.D. df=1.0 µm)

: 40˚C (5 min) -7˚C/min -220˚C (5 min)

: 250˚C: He 100 kPa

: EI: m/z 29 - 300: See Table 2.26.1

Purge & TrapTrap TubePurge TemperaturePurge TimePurge Flow RateDesorption Temperature

: GL Trap1: 35˚C: 2.5 min: 30 mL/min: 200˚C

Environment Water

87

2.27 Reducing Time for the Analysis of VOCs in Water using Purge&Trap GC/MS - GC/MS

■ ExplanationMeasurements of trihalomethanes in swimming pool water(2001 Ministry of Health, Labour and Welfare Notification)are conducted by Purge&Trap GC/MS intensively duringthe summer swimming season. As this analysis takes 40minutes per sample and samples cannot be stored for longperiods of time, reducing the analysis time and achievingstable sensitivity were important issues facing this type ofanalysis. This section introduces an example of reducing thetime required for the analysis of 23 VOCs in water. Fig.2.27.1 shows the total ion chromatogram of 23 VOCs (5µg/L concentration). This system can measure the 23 VOCsat 20-minute intervals. This represents a significant timereduction over the previous analytical conditions (40minutes). With this system, the component peaks becomecloser together as the analysis time decreases, making itdifficult to set the selected ion monitoring (SIM) conditions.Consequently, these measurements were done in the Scanmode. Measurements in the Scan mode were able to detectall 23 VOCs at 0.1 µg/L concentration. Fig. 2.27.2 showsthe mass chromatograms for 0.1 µg/L bromoform, whichhas the lowest relative sensitivity of the 23 VOCs.


-P&T-Trap TubeSample VolumeSample TemperaturePurge TimePurge Flow RateDry Purge TimeDesorption TimeBake Temperature

-GC-Column

Column TemperatureCarrier Gas

-MS-Interface Temperature Ion-Source TemperatureScan RangeScan Interval

: TEKMAR DOHRMANN 4000J (with HTP rapid-analysis set for Tekmar 4000J)

+ GCMS-QP2010

: AQUA Trap 1: 5 mL : 40˚C: 4 min: 40 mL/min: 2 min: 4 min Desorption Temperature: 260˚C: 270˚C Bake Time: 5 min

: AQUATIC-H (30 m × 0.32 mm I.D.df=1.4 µm)

: 35˚C (3 min) -20˚C/min -235˚C : He, 50 kPa

: 200˚C : 200˚C : m/z 45-300: 0.5 s

min

1,688,561

4.0 5.0 6.0 7.0 8.0 9.0 9.9

TIC

1 23 4 5 6 7

8

9

10

1112

13

14

1516

17

18

19

20

21

IS

22

4,165

4,165

8.2 9.0

173

171 1 171.00 2090 55.00

ID# : 21m/z : 173.00Type : TargetName : BromoformR.T. : 8.613Area : 8218 # m/z Intensity Ratio %

No. Compound Name1234 56789 1011

1,1-DichloroethyleneDichloromethanetrans-1,2-Dichloroethylenecis-1,2-Dichloroethylene Chloroform1,1,1-TrichloroethaneCarbon TetrachlorideBenzene1,2-Dichloroethane Trichloroethylene1,2-Dichloropropane

No. Compound Name1213141516171819202122

Bromodichoromethanecis-1,3-DichloropropeneToluenetrans-1,3-Dichloropropene1,1,2-TrichloroethaneTetrachloroethylene Dibromochloromethanem,p-Xyleneo-XyleneBromoformp-Dichlorobenzene

Table 2.27.1 Names of VOCs

Fig. 2.27.1 Total ion chromatogram for 23 VOCs (5 µg/L concentration) Fig. 2.27.2 Mass chromatograms for 0.1 µg/L bromoform

88

2.28 Analysis of Estradiol - GC/MS

■ Explanation17 β-Estradiol is monitored using GC/MS because it is achemical substance suspected of having an endocrinedisrupting effect. Electron ionization is used as theionization mode for MS, but this data introducesmeasurements taken using negative chemical ionization(NCI).

ReferenceShimadzu Application News No. M198


Column Temperature

Injection Inlet TemperatureCarrier GasInjection MethodInjection VolumeMSIonizationScan RangeMonitored Mass

: DB-5H (30 m × 0.25 mm I.D. df=1.0 µm)

: 50˚C (2 min) -20˚C/min -250˚C -5˚C/min -300˚C (5 min)

: 280˚C: He 120 kPa : Splitless (2.0 min/250 kPa): 2 µL

: NCI (Isobutane): m/z 29 - 700: 343, 269, 367, 431, 347

Water Sample

1L water sample


Elution

Desiccation

Hexane layer dehydrating, exsiccation

TMS derivatization

Silica gel mini column

GC/NCI-MS

Surrogate addition

C18 cartridge

5mL methanol

N2 purge

0.5mL PFB reaction liquid

Anhydrous Na2SO4 & N2 purge

TMS imidazole

pH 5 acetate buffer

Cleaning using 5mL purified water & 5mL hexane

6mL water, 2mL hexane

Hexane washing

Hexane: Ethyl acetate (9:1) elution

PFB derivatization

Sediment & Organism Sample

10g sample

Extraction

Methanol/hexane distribution

Dichloromethane extraction

Desiccation

PFB derivatization

Hexane layer dehydrating, desiccation

Florisil column

TMS derivatization

Silica gel mini column

GC/NCI-MS

Surrogate additive

Solid-phase extraction of sediment

Florisil/C18 cartridge

GPC column, etc.

N2 purge

0.5mL PBB reaction liquid

Anhydrous Na2SO4 & N2 purge

TMS imidazole

Methanol & pH acetate buffer (9:1)

Take methanol layer and add water

6mL water, 2mL hexane

Hexane washing


Hexane washing


Purifying prior to derivatization

HO

OH OH

O

FF

F

FFPFB derivatization

O

O

FF

F

FF

Si

TMS derivatization

17 -Estradiol

650000006000000055000000

5000000045000000400000003500000030000000250000002000000015000000100000005000000

0

a-estradiol

Estoron-estradiol + d

Ethynyl estradiolEstriol

13 14 15 16 17 18 19 20 min

TIC *1.00343.20 *1.54269.10 *1.50347.30 *1.76367.20 *1.63431.30 *1.77


Fig. 2.28.2 Derivatization Fig. 2.28.3 Total ion chromatograms of estradiol types

89

3.1 Analysis of Anions in Wastewater - Ion Chromatograph

■ ExplanationFluorine, nitrate nitrogen and nitrite nitrogen are raised asnecessary monitoring items in the water environmentstandards, and the ion chromatograph method is one of themonitoring methods employed. Inorganic ions inwastewater are one of the causes of pollution andeutrophication in rivers and lakes, and pollution isapproaching a critical stage due to abnormal drought inrecent years and neglect in the area of sewage facilityprovision. Thus, the importance of monitoring inorganicions in wastewater has increased.



Fig. 3.1.1 Analysis of wastewater

■ Peaks

1 PO43 –

2 Cl–

3 NO3–

4 SO42 –

Instrument

ColumnMobile Phase

Flow RateTemperatureDetector


: Shim-pack IC-A1 (100mmL. × 4.6mm I.D.): 2.5 mM Phthalic Acid

2.4 mM Tris (Hydroxymethyl)Aminomethane


3. Wastewater

90

3.2 Analysis of Volatile Organic Compounds (VOCs) in Wastewater - GC0

.0

8.0

10

.0

12

.0

30

.0

32

.0

14

.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

1,1

-Dic

hlo

roe

thy

len

e

1,1

-Dic

hlo

roe

thy

len

e

Dic

hlo

rom

eth

an

e

Dic

hlo

rom

eth

an

e

tra

ns

-1,

2-D

ich

loro

eth

yle

ne

cis

-1,

2-D

ich

loro

eth

yle

ne

Ch

loro

form

1,

2-D

ich

loro

eth

an

e1

, 1

, 1

-Tri

ch

loro

eth

an

e

Ca

rbo

n t

etr

ac

hlo

rid

e

Dib

rom

oc

hlo

rom

eth

an

e

Te

tra

ch

loro

eth

yle

ne

Bro

mo

form

p-D

ich

loro

be

nz

en

e

1,2

-Dic

hlo

rop

rop

an

e

Bro

mo

dic

hlo

rom

eth

an

e

cis

-1,

3-D

ich

loro

pro

pe

ne

tra

ns

-1,

3-D

ich

loro

pro

pe

ne

1,

1,

2-T

ric

hlo

roe

tha

ne

★

★

★

★

★

Tri

ch

loro

eth

yle

ne

★

★★

★

★

★

Fig. 3.2.1 Analysis example of VOCs in environment water using headspace GC-ECD (* signifies regulated item of wastewater standard)

■ ExplanationEnvironment water analysis is mostly conducted usingGC/MS, but GC can be used for analyzing just thosesamples that have small amounts of impurities in them.This data is an example of analysis for water with VOCsusing head space GC. This method can be used to analyze10 of the items in the items of the wastewaterstandard.Benzene needs to be analyzed using FID as itcannot be detected by ECD.


Column TemperatureInjection Inlet TemperatureDetectorCarrier GasHeadspace ThermostattingHeadspace Injection Volume

: HSS-4A + GC-17AAE: DB-VRX (75 m × 0.45 mm I.D.

df=2.55 µm): 35˚C (5 min) -5˚C/min-180˚C: 200˚C: ECD 210˚C: He 6.0 mL/min: 50˚C, 60 min: 0.2 mL (Direct Injection)

Wastewater

91

3.3 Analysis of Inorganic Components in Wastewater (1) - ICP/MS

■ ExplanationWastewater samples comprise several matrices, includingorganic components, alkaline elements, and alkaline earthelements. These matrices differ significantly depending onthe wastewater discharge location and type of industry.Consequently, a highly sensitive analysis method thatsuffers from little interference is required to accuratelyanalyze trace elements in wastewater. This sectionintroduces the results of the analysis of factory wastewaterusing Shimadzu ICPM-8500.

■ SamplesFactory wastewater A, B

■ PretreatmentAdd 2 mL ultra-pure-grade nitric acid (Tama ChemicalsAA-100) to 50 mL sample solution. Thermally decomposethe mixture using the microwave oven in power mode.After cooling, make up to 50 mL to produce the analysissample. Spike this analysis sample with the target elementsto make the standard spiked sample.

■ Quantitative AnalysisThe analysis sample and standard spiked sample wereanalyzed using the internal standard method – calibrationcurve method. . Internal standard elements

The internal standard elements were spiked online usingADU-1 Automatic Sample Dilution unit.

Table 3.3.1 shows the quantitation results and recoveryrates. A satisfactory recovery rate was achieved for eachelement.


: ICPM-8500

: 1.2 kW: 7 L/min: 1.5 L/min: 0.58 L/min

: Coaxial Nebulizer: 0.5 mL/min: Cooled Scott Chamber: Three-layered Mini Torch: 3.5 mm: Copper

References(1) JIS K0102-1998 Testing Methods for Industrial Wastewater(2) Partial revision of Ordinances of Water Pollution

Prevention Law Related to Environmental Standards, 8 March 1993

(3) Microwave Assisted Acid Digestion Of Siliceous And Organically Based Matrices (EPA Method3052)

(4) EPA Method200.8 Ver.5.4 Date : F06/26/98

92

3.3 Analysis of Inorganic Components in Wastewater (2) - ICP/MS

Wastewater A

Element Quantitationvalue

* Recoveryrate (%)

Wastewater B

Quantitationvalue

* Recoveryrate (%)

** Spikedvolume

Wastewaterstandard

*Recovery rate : Recovery rate (%) determined by spike and recovery tests (** spiked volume).

Table 3.3.1 Quantitation results on wastewater (units: mg/L)

93

4.1 Analysis of Acidic Substances in Exhaust Gas - Ion Chromatograph

■ ExplanationAnalysis of acidic gas existing in exhaust gas wasperformed. The analysis targets, HC1, NOx, and SOx, wereindividually absorbed into absorption solutions, thenanalyzed by an ion chromatograph. Figure 4.1.1 shows theresults for analysis of a solution obtained by absorbing HC1from exhaust gas into 0.4 % NaOH. Figure 4.1.2 shows theresults for analysis of NO3

– created by absorbing NOx fromexhaust gas into a mixed solution H2O2 and Sulfuric acid.Figure 4.1.3 shows the results for analysis of SO4

2– createdby absorbing SOx from exhaust gas into H2O2. All threesamples can be measured at high sensitivity without anyspecial pretreatment.

Fig. 4.1.1 Analysis of HC1 in exhaust gas Fig. 4.1.2 Analysis of NOx in exhaust gas Fig. 4.1.3 Analysis of SOx in exhaust gas



ColumnGuard ColumnMobile Phase



: Shim-pack IC-A3 (150 mmL. × 4.6 mm I.D.): Shim-pack IC-GA3 (10 mmL. × 4.6 mm I.D.): 5.0 mM p-Hydroxybenzoic Acid



■ Peaks

1 Cl–

(95.6ppm)

2 SO42 – (66.1ppm)

■ Peaks

1 Cl–

(0.42ppm)

2 NO3–

(1.98ppm)

3 SO42 – (9.14ppm)

■ Peaks

1 Cl–

(49.0ppm)

2 SO42 – (7.94ppm)

4. Atmosphere

94

4.2 Analysis of Tolylenediisocyanate (TDI) in Work Environment Monitoring (1)- LC

2,6-TDI

0

0

0.5

mAbs

2 4 (min)6 8

2,4-TDI

Reagent decomposition matter

Fig. 4.2.1 Analysis of TDI gas sample (equivalent to 0.5 ppb each)

■ ExplanationIn 1995, partial amendments were made to the workenvironment evaluation standard and the work environmentmonitoring standard. High performance liquid chromatographywas added to the analysis methods currently being used forethyleneimine, 3, 3'-dichloro-4, 4'-diaminodiphenylmethane,and tolylenediisocyanate (TDI). Among these TDI is greatlyused in materials such as the raw material of polyurethanefoam, cross linking agents for polymerization, foamingagent, paints, and glues, and is strongly toxic to the humanbody, which, in cases of acute poisoning, can causepneumonia and tuberculosis, that can lead to fatalities dueto weakening of the heart if the illness becomes serious.Currently, the value for the work environment standard hasbeen amended to 5 ppb, and a measurement level of onetenth of this, 0.5 ppb, is requested. Here, a suitable testingmethod is the high performance liquid chromatographmethod, which is highly sensitive in comparison toconventional diazotization coupling absorptiometry, andhas many features such as the capability of being able toseparately quantify isomers.

ReferenceKenji Nakaaki, Shinya Koike, Yuriko Takada: LaborScience, 63 (1), 1-13, 1987

■ PretreatmentAfter collecting a sample for 10 min in 1-(2-pyridyl)piperazine impregnated filter paper at a gas suction flowrate of 1 L/min, remove sampling filter paper, and extractsample using a shaker with 4mL of methanol containingacetic acid. Filter the extracted solution through a 0.45 µmmembrane filter to make a test solution.



: LC-VP System: STR ODS-II (150 mmL. × 4.6 mm I.D.): 50 mM Sodium Acetate Buffer Solution

(pH 6.2)/Acetonitrile = 68/32 (v/v): 1.5 mL/min: 40˚C: UV Absorbance Detector 247 nm

Atmosphere

95

4.2 Analysis of Tolylenediisocyanate (TDI) in Work Environment Monitoring (2)- LC

Sampling and Pretreatment Method

Sample 10 L

Sampling

Collect sample for 10 min in 1-(2-pyridyl) piperazine

impregnated filter paper at a gas suction flow rate

of 1 L/min.

Add 4 mL of methanol (containing acetic acid of 0.05 v/v%)

and shake for 30 min.

Extraction

Filtration

Use a 0.45 µm membrane filter.

HPLC 20 µL Injection

Nitrogen cylinder

Nitrogen cylinder Standard gas generator

Glass board for sampling

Solid-phase collecting

Humidity sensor

Exhaust

Trap

Humidification device

Sample provided by Japan Work Environment Monitoring Association.

Flow Diagram for TDI Generation Device

96

4.3 Analysis of Aldehyde/Ketonic products in Exhaust Gas - LC

■ ExplanationThis shows an example of analysis performed onaldehyde/ketonic products found in vehicle exhaust gas.In cases where exhaust gas is set as the sample, andreversed phase chromatography is used to separate anddetect absorbance, the type of impurities and the amountof content often lead to difficulties in analysis. Inparticular, impurity peaks are sometimes observed aspeak overlay and warping for formaldehyde peaks that iseluted out quickly. In such cases, these affects can beavoided by adding methanol to mobile phase A solution.Sample kindly lent by Traffic Safety and NuisanceResearch Institute of the Ministry of Transport.

3.00.0 9.06.0 15.012.0 21.018.0 27.024.0

(min)

1

23

■ Peaks1. Formaldehyde2. Acetone3. 2-Butanone

Fig.4.3.1 Analysis of aldehyde/ketonic products in exhaust gas



: LC-VP System: STR ODS-II (150 mmL. × 6.0 mm I.D.): A / B Gradient Elution Method

A: Water/THF/Methanol = 70/10/20 (v/v/v)

B: Water/Acetonitrile = 30/70 (v/v): 1.0 mL/min: 45˚C: UV-VIS Absorbance Detector 365 nm

Atmosphere

97

■ ExplanationWith regard to the monitoring regulations and analysismethods for harmful pollutants in the air, the AmericanEnvironmental Protection Agency (EPA) has already listedrecommended analysis methods for 189 compounds withthe Clean Air Act. Here, an example of analysis of generalresidential room air in accordance with the aldehydeanalysis method recommended by the EPA is introduced.

■ PretreatmentSample air was made to pass through silica gel cartridgecoated with dinitrophenylhydrazine (DNPH) in acidifiedstate, after trapping each aldehyde/ketonic product asDNHP derivatives, they were extracted by eluting out with anorganic solvent. This enables high-scale concentration. Inthe case of this sample, the DNPH cartridge was attacheddirectly to an on-site sampling pump (SHIMADZU VPC-10), the sample concentrated, and eluted out withacetonitrite to make the test solution.

■ Analytical ConditionsDeviceColumnMobile Phase


: LC-VP System: STR ODS-II (150 mmL. × 6.0 mm I.D.): A / B Gradient Elution Method

A: Water/THF/Methanol = 70/10/20 (v/v/v)

B: Water/Acetonitrite = 30/70 (v/v): 1.0 mL/min: 45˚C: UV-VIS Absorbance Detector 365 nm

(min)

0.0 4.0 8.0 12.0 16.0 20.0 24.0 28.0 32.0

1

32

4

5

6 7 8

9

■ Peaks1. Formaldehyde2. Acetaldehyde3. Acrolein4. Propionaldehyde5. Methacrolein6. n-Butyraldehyde7. Benzaldehyde8. Valeraldehyde9. Hexanaldehyde

Fig. 4.4.1 Analysis of aldehyde/ketonic products in room air

4.4 Analysis of Aldehyde/Ketonic products in Atmosphere (1) - LC

98

2nd analysis of room air(Acetone in use)

1st analysis of room air

Cartridge blank

Fig. 4.4.2 Analysis example of formaldehyde in room air

4.4 Analysis of Aldehyde/Ketonic products in Atmosphere (2) - LC



: LC-2010: Shim-pack FC-ODS (75 mmL. × 4.6 mm I.D.): A / B Gradient Elution Method: A: Water/THF = 8/2 (v/v): B: Acetonitrile: 1.2 mL/min: 40˚C: UV-VIS Absorbance Detector 365nm

Atmosphere

99

4.5 Analysis of Aldehydes in Atmosphere (1) - GC

■ ExplanationThere are 13 kinds of harmful air pollutants (substances thatcan be harmful to human health if in imbibed on a regularbasis and cause actual air pollution), and this sectionintroduces the air-borne aldehyde products. Under theOffensive Odor Control Law, factories are obligated tomonitor aldehydes at their site perimeters.

ReferenceActual Monitoring of Harmful Air Pollutants 157 – 200(1997) Environment Agency, Air Quality Bureau, AirRegulation Section Edition

DPA

(IS

)

Fo

rm

Ace

t

Ace

ton

eP

rop

ion

i-B

uty

rM

EK n

-Bu

tyr

i-V

aler

n-V

aler

MIB

K

0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 (min)

Fig. 4.5.1 Analysis example of aldehyde DNPH products

DPA

(IS

)

Fo

rm

Ace

t

Ace

ton

eP

rop

ion

i-B

uty

r

ME

Kn

-Bu

tyr

i-V

aler

n-V

aler

MIB

K

0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 (min)

Fig. 4.5.2 Analysis example of aldehyde products in the environment

This is an example of analysis of formaldehyde,acetaldehyde together with elements(propionaldehyde, butyraldehyde, andvaleraldehyde) targeted by the Offensive OdorControl Law, as well as ketonic substances thatreacts with DNPH. Diphenylamine (DPA) wasused as the internal standard substance (Fig. 4.5.1).

This shows an example of actual air collectedand analyzed (Fig. 4.5.2).

■ PretreatmentAir-borne aldehyde is changed to a derivative (aldehydeDNPH) using 2, 4-dinitrophenylhydrazine when concentratedand collected, and is measured using FTD (thermal ionizationdetector) which is highly sensitive and selective againstnitrogen compounds.

■ Analytical ConditionsColumnColumn Temperature

Injector Inlet TemperatureDetector TemperatureCarrier GasInjection Method

: DB-1 (30 m × 0.25 mm I.D. df=0.25 µm): 80˚C (2 min) -20˚C/min-90˚C

-3˚C/min-230˚C: 250˚C: 280˚C (w-FTD): He 2.9 mL/min: Splitless (1 min)

100

4.5 Analysis of Aldehydes in Atmosphere (2) - GC

Pretreatment Method

■ Sample Collection MethodTwo marketed cartridges impregnated with 2, 4-dinitrohydrazineare used in tandem. Pump flow rate is set to be about 0.1 L perminute, and collection is performed continuously for 24 hours.The used air volume is measured with a flowmeter. To preventthe breakup of aldehyde DNPH by air-borne ozone, an ozonescrubber cartridge is attached to the front of the collectioncartridge system (Fig. 4.5.3).

■ Cartridge Eluting Out MethodAldehydes react in the cartridges to form aldehyde-DNPHs,and are eluted out using acetonitrile. Unreacted DNPH isalso eluted out at this time using a positive ion exchangeresin as it can interfere with analysis. As the eluting outsolvent acetonitrile is sensitive to FTD, it is solved intoethyl acetate to make a sample solution (Fig. 4.5.4).

Fig. 4.5.3 Sample collection method Fig. 4.5.4 Eluting out method from cartridge

Atmosphere

101

4.6 Analysis of Formaldehyde in Room Atmosphere - UV

■ ExplanationFormaldehyde residue sometimes exists in wall materialsand flooring of homes, and this residue is dispersed as avapor in house air. Consequently, monitoring theconcentration of such formaldehyde has become animportant task. Here, experimental monitoring wasperformed in the rooms of a new house using a combinationof a solution collection method with water and anacetylacetone colorimetric method.

ReferenceJIS K0303-1993 Monitoring of HCHO in exhaust gas

■ Monitoring DeviceConcentrated Collection DeviceSpectrophotometer

: VPC-10: UV-1600 Standard

Glass Cell

//

//

//

/

//

//

//

/

//

/ /

Heat for 30 min in heating solution (40+2˚C)

Keep at room temperature for 30 min

5 mL of purifying water for creation of calibration curve

5 mL of formaldehyde STD

5 mL of test solution for concentration measuring

5 mL of test solution

Sample BLMeasured sampleSTDReagent BL

Wavelength : 412.0Slit width : 2.0

Multi-point calibration curveConc=K1 A+K0K1=3.762 k0=0.00526

Chi-Square : -0.00118Data points : 6

ID Concentration Absorbance1 0.08126 0.0201 0.08051 0.020Average : 0.08088 0.020 /Room 1 results (in absorption solution)Standard deflection : 2 0.1452 0.0372 0.1459 0.037Average : 0.1456 0.037 /Room 2 results (in absorption solution)Standard deflection :3 0.06170 0.0153 0.05793 0.014Average : 0.05981 0.014 /Room 3 results (in absorption solution)Standard deflection :

Measurement results for formaldehyde in air

Room 1: 0.302 ppm (20 min)Room 2: 0.272 ppm (40 min)Room 3: 0.223 ppm (20 min)

Put 40 mL volumes of absorption solution (distilled water) into absorption beakers 1 & 2.

Sampling (flow rate 1 L/min, collection time 20 or 40 min)

Retrieve absorption solution, and measure up to 100 mL with distilled water.

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

µg/mL

1.0001.100

0.000

0.500

1.000 2.000 3.000 4.500

Absorbance

Standard sample

–

Fig. 4.6.1 Measuring flow chart for formaldehyde in air

Fig. 4.6.2 Measuring example of formaldehyde in air

102

4.7 Analysis of Volatile Organic Compounds (VOCs) in Atmosphere(1)- Solid-phase Adsorption & Thermal Desorption GC/MS

■ ExplanationVarious substances that are harmful to human health arebeing found in ambient air, and though the concentrationsmay not be enough to harm human health directly, there arefears that exposure over time can lead to cancer, etc. Withthis as a background consideration, a law partially amendingthe Air Pollution Control Law was introduced in May 1996,and put into practice from April 1st, 1997. The CentralCouncil for Environmental Pollution Control published viathe second verdict in October 1996 a list of 234 substancesthat are potentially harmful air pollutants (HAPs), amongwhich 22 types are listed as being substances that requirepriority action. In February 1997, an environment standardfor annual average of benzene 0.003 mg/m3, trichloroethene0.2 mg/m3, tetrachloroethene 0.2 mg/m3, in April 2001,dichloromethane 0.15 mg/m3 was announced to cover airpollution. The analysis method for monitoring this standardinvolves solid-phase adsorption and thermal desorption. Theanalysis in this method involves sampling VOCs in theatmosphere for 24 hours using a tube.

–– Tube ––This is comprised of a glass or stainless tube filled withadsorption material. The adsorption material is graphitecarbon black, carbon molecular sieves. These are used inmultiple bed form to match targeted sample.

References(1) Actual Measuring of Harmful Air Pollutants

Publisher: Editing Committee for Actual Measuring ofHarmful Air Pollutants, May 2000

(2) Manual of Measuring of Harmful Air PollutantsEnvironment Agency, Air Quality Bureau, AirRegulation Section Edition, April 1997

Fig. 4.7.1 Sampling with tube collection method

Fig. 4.7.2 Continuous air sampler

Dehydration tube

Flowmeter Suctionpump

Adsorption tubeAmbient air

Atmosphere

103

4.7 Analysis of Volatile Organic Compounds (VOCs) in Atmosphere (2)- Solid-phase Adsorption & Thermal Desorption GC/MS

■ Analytical ConditionsThermal Desorption

Collection Tube DesorptionDesorption Flow RateSecond Trap DesorptionOutlet Split

: 280˚C (5 min): 50 mL/min: 280˚C (2 min): 8 mL/min

Shimadzu GCMS-QP5050AColumnColumn Temperature

Carrier Gas

: DB-1 (60 m × 0.32 mm I.D. df=5 µm): 40˚C (5 min)-5˚C/min-150˚C

-10˚C/min-250˚C (5 min): He 100 kPa

5 10 15 20 25 30 35 (min)

MIC 2000000

Freo

n 12

Eth

anol

Dic

hlor

omet

hane

n-H

exan

e

Chl

orof

orm

Ben

zene

Tolu

ene

Eth

yl b

enze

nem

, p-X

ylen

e

Sty

rene

6 8 10 12 14 16 18 20 22 24 26 (min)

2

13

4

5

6

7

8

9

TIC 127756ID

1

2

3

4

5

6

7

8

9

Name

Chloroethene

1,3-Butadiene

Acrylonitrile

Dichloromethane

Chloroform

1,2-Dichloroethane

Benzene

Trichloroethene

Tetrachloroethene

Fig. 4.7.3 Analysis example (SIM method) of 9 HAPs elements (1 ppm × 10 mL)

Fig. 4.7.4 Analysis example (SCAN method) of lab air

104

4.8 Analysis of Volatile Organic Compounds (VOCs) in Atmosphere (1) - Container Collection Method GC/MS

■ ExplanationVarious substances that are harmful to human health arebeing found in ambient air, and though the concentration maynot be enough to harm human health directly, there are fearsthat exposure over time can lead to cancer, etc. With this as abackground consideration, a law partially revising the AirPollution Control Law was introduced in May 1996, and putinto implementation from April 1st, 1997. The CentralCouncil for Environmental Pollution Control published viathe second verdict in October 1996 a list of 234 substancesthat are potentially harmful air pollutants (HAPs), amongwhich 22 types are listed as being substances that requirepriority action. In February 1997, an environment standardfor annual average of benzene 0.003 mg/m3, trichloroethene0.2 mg/m3, tetrachloroethene 0.2 mg/m, in April 2001,dichloromethane 0.15 mg/m3 was announced to cover airpollution. The analysis method called container collection

5 10 15 20 25 30 (min)

1

2

3

4

5

6

7

8

9

1011

12

13 1415

16

17

18

19

20

21

22

IS

23

24

25

26

30

29

28

27

31

32

33

34

3536

37

38

39

40

MIC 84230717

Fig. 4.8.1 EPA TO14+2 elements (1, 3-butadiene, acrylonitrile) 10 ppb

1

2

3

4

5

6

7

8

9

10

11

12

13

14

Freon12

Freon114

Chloromethane

Chloroethene

1,3-Butadiene

Bromomethane

Chloroethane

Freon11

Freon113

1,1-Dichloroethene

Acrylonitrile

Dichloromethane

1,1-Dichloroethane

cis-1,2-Dichloroethene

15

16

17

18

19

20

21

22

23

24

25

26

27

28

Chloroform

1,1,1-Trichloroethane

Carbon tetrachloride

1,2-Dichloroethane

Benzene

Trichloroethene

1,2-Dichloropropane

cis-1,3-Dichloropropene

Toluene

trans-1,3-Dichloropropene


Tetrachloroethene

1,2-Dibromoethane

Chlorobenzene

29

30

31

32

33

34

35

36

37

38

39

40

IS

Ethylbenzene

m,p-Xylene

o-Xylene

Styrene


1,3,5-Trimethylbenzene

1,2,4-Trimethylbenzene

m-Dichlorobenzene

p-Dichlorobenzene

o-Dichlorobenzene

1,2,4-Trichlorobenzene

Hexachloro-1,3-butadiene

Toluene-d8

involves the use of a collection canister (inert processedmetal airtight sealing) used to sample the VOCs in theatmosphere for 24 hours.

–– Canister ––The canister is an airtight, spherical container, which isspecially processed to be inert by being formed from ametal construction with electro polished inner surface andpure chrome-nickel oxide thin film (SUMMA®).

References(1) Actual Measuring of Harmful Air Pollutants

Publisher: Editing Committee for Actual Measuring ofHarmful Air Pollutants, May 2000

(2) Manual of Measuring of Harmful Air PollutantsEnvironment Agency, Air Quality Bureau, Air PollutionControl Edition, April 1997

105

4.8 Analysis of Volatile Organic Components (VOC) in Atmosphere (2)- Container Collection Method GC/MS

Standby

Sample pressure check

Trap baking

Sample ready

Trap cooling

Internal standard sample concentration

Sample concentration

Dry barge

Cryofocusing

Trap preparation heating

Trap desorption

Cryo trapAnalysis time wait

Trap, MCS baking

Sample pressure checkYes

None

Cryo inject

Trap, MCS baking

Standby

Next sample

Fig. 4.8.3 AUTOCanTM analysis flow chart

Ambient Air Collection Method using CanisterThe canister is cleaned before being used for sampling, andset to vacuum state ready for sampling. The following twomethods are used for long-period collection of ambient air.♦ Passive sampling method

The difference in pressure between the atmosphere andcanister are used, and the passive sampler adjusted to takesamples.

♦ Pressurization collection methodAmbient air is sent in by metal bellows pump, and thepassive sampler adjusted to take samples.

■ Analytical ConditionsTEKMAR-DOHRMANN AUTOCanTM

Concentration TemperatureSample VolumeDesorption TemperatureDesorption TimeCryofocusInjection Time

: -100˚C: 400 mL: 220˚C: 2 min: -185˚C: 2 min

Shimadzu GCMS-QP5050ACarrier GasColumn

Column Temperature

: He 110 kPa: AQUATIC (60 m × 0.25 mm I.D.

df=1 µm): 40˚C-3.5˚C/min-120˚C-6˚C/min

-180˚C-20˚C/min-220˚C (6 min)

Control valve

Passive sampling methodFlow controller

Pressurizedcollection method

Fig. 4.8.2 Ambient air collection method using canister

6 8 10 12 14 16 18 20 22 (min)

1

2

3

4

5

68

7

IS

9

MIC 184363

Fig. 4.8.4 9 HAPs elements (elements from the 22 priority substances that can be simultaneously analyzed) 0.1 ppb

ID12345678IS9

NAMEChloroethene1,3-ButadieneDichloromethaneAcryonitrileChloroform1,2-DichloroethaneBenzeneTrichloroetheneToluene-d8Tetrachloroethene

Atmosphere

106

Fig. 4.9.1 Flow channel configuration diagram

Fig. 4.9.2 Chromatograms of N2O Fig. 4.9.3 Example of continuous analysis of N2O in atmosphere

V1 : 10way-rotary valve

V2 : 4way-rotary valve

PC : Pre Column

MC : Main Column

DC : Dummy Column

CC : Choke Column

SV : Solenoid Valve

Time

4.9 Automatic Analysis of Micro Amount of N2O in Atmosphere - GC

meantime, components containing N2O are separated inmain column 1, and once the quickly eluting air passesthrough a choke column (CC2) and is discharged out of thesystem, V2 switches to the full line, and the targeted N2O issent to main column 2 for detection by the ECD. Fig. 4.9.2and Fig. 4.9.3 show the chromatograms and continuousanalysis results.

References(1) Examples of Shimadzu System Gas Chromatograph(GC-S135) (2) Shimadzu Application News No. G161

■ Analytical ConditionsAnalysis TimeCarrier Gas

: 15 min: Argon + Methane

■ ExplanationIt is believed that nitrous oxide (N2O) exists in theatmosphere at approximately 300 ppb. ECD is employed asthe detector for analysis using a gas chromatograph, andprolonged stable use of this detector is required forautomatic analysis, which means that the following arerequired of a system configuration.1) Highly pure carrier gas2) Use of a well conditioned column3) Oxygen cannot enter ECD4) Use of flow channel components that do not affect ECD5) Removal of non-essential components in sampleFig. 4.9.1 shows the flow channel configuration of theanalysis system. Firstly, after collection of ambient air insampling tube, valve V1 is switched from a full line to abroken line to induct atmosphere components into the pre-column. At the point when air, CO2 and N2O transfer to themain column, V1 returns to the full line, and water (whichis an impurity) is discharged out of the system. In the

Concentration ppm

Atmosphere

107

4.10 Analysis of Inorganic Components in Atmospheric Dust - ICP-AES

■ Analytical ConditionsInstrumentRF OutputCoolant Gas Flow Rate Plasma Gas Flow Rate Carrier Gas Flow Rate Sample Introduction ChamberPlasma TorchObservation Method

: ICPS-7510: 1.2 kW: 14 L/min: 1.2 L/min: 0.7 L/min: Coaxial Nebulizer: Cyclone Chamber: Standard Torch: Axial

■ ExplanationInorganic components in atmospheric dust were analyzedusing ICPS-7510. The solution processed throughdecomposition process was inducted to the ICP, andqualitative analysis performed. Table 4.10.1 shows thequantitation results. Fig. 4.10.1 shows the calibrationcurves.

■ SampleNIST SRM1648 Urban Particulate Matter Standard

■ PretreatmentAdd 10 mL of nitric acid, 3 mL of hydrogen peroxide, 5 mLof hydrofluoric acid to 0.2 g of sample, and decomposeusing a microwave high-speed sample decompositiondevice. Evaporate until dry over a hotplate, then dissolve(1 + 1) with 5 mL of nitric acid, and measure up to 100 mL Table 4.10.1 Quantitation results on atmospheric dust (units: µg/g)

Fig.4.10.1 Calibration curves

SD

Correlation

Units

SD

Correlation

Units

SD

Correlation

Units

Coefficients : Coefficients : Coefficients :

Element

Ni

As

Be

Mn

Cr

Pb

Cd

Measured value

85.0

123

2.45

815

402

6500

77.0

Certified value

82 ± 3

115 ± 10

(860)

403 ± 12

6550 ± 80

75 ± 7

108

4.11 Analysis of Inorganic Components in Atmospheric Dust (1)- ICP/MS


: IPCM-8500

: 1.2 kW: 7 L/min: 1.5 L/min: 0.62 L/min


■ ExplanationAs long-term exposure to toxic contaminants in the ambientatmosphere can be detrimental to human health, it isimportant to gain a sound understanding of theconcentrations of contaminants in the atmosphere.Following the Water Pollution Prevention Law, the AirPollution Prevention Law was partially revised in 1996 toincorporate countermeasures to toxic contaminants in theatmosphere. These cover 22 inorganic substances, of whichAs, Ni, Mn, Cr6+, Be, and Hg are given priority. Thissection introduces an example of the analysis of As, Ni,Mn, Cr, and Be, as well as two other controlled substances:Pb and Cd. The calibration curve method was used for thesemeasurements. Table. 4.11.1 shows the quantitation results.The results match well with the certified values.

■ SampleNIST SRM1648 Urban Particulate Matter Standard

■ Pretreatment(1) Weigh 0.2 g sample into a fluororesin decomposition

vessel. Add 10 mL nitric acid, 3 mL hydrogen peroxide,and 5 mL hydrofluoric acid and leave for approximately4 hours (preliminary reaction).

(2) Subject this mixture to two approximately 30-minutedecomposition sequences in the microwave oven.

(3) After the internal pressure in the decomposition vesseldrops below about 40 psi, carefully open the lid.

(4) Transfer the liquid into a fluororesin beaker and heat ona hot plate (approx. 190˚C) until it almost dries andhardens.

(5) Add 10 mL dilute (1+10) nitric acid and heat until italmost dries and hardens.

(6) Add 5 mL nitric acid (1+1) and 10 mL ultrapure waterand heat for about 1 hour until all solids are dissolved.

(7) Transfer the solution to a polyethylene container andmake up to 100 mL with purified water.

Dilute this solution 50 times with ultrapure water. Spike with 50 ppb each of Co, Y, Rh, and Tl as internalstandard elements to produce the analysis sample.

Sample decomposition unitMicrowave OvenModel 7195 Microwave Oven with temperature controller, manufactured by O.I. Analytical.

■ Calibration Curve SampleMix AA-grade standard solution (1000 ppm) and thendilute as appropriate with ultrapure water. Spike with 50ppb internal standard elements and add 1% nitric acid.

References(1) Hazardous Air Pollutants Measurement Manual (Air

Pollution Control Division, Air Quality Bureau,Environment Agency, March 1999)

(2) Work Environment Measurement Guidebook 4 Metals(Japan Association for Working EnvironmentalMeasurement, 20 September 2005)

Atmosphere

109

4.11 Analysis of Inorganic Components in Atmospheric Dust (2)- ICP/MS

Fig. 4.11.1 Calibration curves for atmospheric dust

Table 4.11.1 Quantitation results on atmospheric dust (units: µg/g)

Element

Quantitation valueCertified value

Measured value (µg/mL) Converted to solid

SD

Correlation

Units

SD

Correlation

Units

Coefficients :

SD

Correlation

Units

Coefficients :

SD

Correlation

Units

Coefficients :Coefficients :

110

4.12 Analysis of Inorganic Components in Fly Ash (1) - ICP/MS


: IPCM-8500

: 1.2 kW: 7 L/min: 1.5 L/min: 0.62 L/min


■ ExplanationInorganic components in coal fly ash were analyzed usingShimadzu ICPM-8500. Quantitation was conducted usingthe calibration curve method. Table 4.12.1 shows thequantitation results converted to concentrations in solids.The results match well with the certified values. Fig 4.12.1shows the mass spectrum.

■ SampleNIST SRM1633-b Coal Fly Ash

■ Pretreatment(1) Weigh 0.1 g sample into a fluororesin decomposition

vessel. Add 10 mL nitric acid, 3 mL hydrogen peroxide,and 5 mL hydrofluoric acid and leave for approximately4 hours (preliminary reaction).

(2) Subject this mixture to a decomposition sequence in themicrowave oven.

(3) After the internal pressure in the decomposition vesseldrops below about 40 psi, carefully open the lid.

(4) Transfer the liquid into a fluororesin beaker and heat ona hot plate (approx. 190˚C) to drive off the hydrofluoricacid.

(5) Immediately before it solidifies, add 10 mL dilute(1+10) nitric acid and heat again until it almost dries andhardens.

(6) Add 5 mL nitric acid (1+1) and 10 mL ultrapure waterand heat for about 1 hour until all solids are dissolved.

(7) Transfer the solution to a polyethylene container andmake up to 100 mL with purified water.

Spike with 50 ppb each of Rh and Te as internal standardelements to produce the analysis sample.

Sample decomposition unitMicrowave OvenModel 7195 Microwave Oven with temperature controller, manufactured by O.I. Analytical.

■ Calibration Curve SampleMix AA-grade standard solution (1000 ppm) and then diluteas appropriate with ultrapure water. Spike with 50 ppb Rhand Te internal standard elements and add 1 % nitric acid.

References(1) Hazardous Air Pollutants Measurement Manual (Air

Pollution Control Division, Air Quality Bureau,Environment Agency, March 1999)

(2) Work Environment Measurement Guidebook 4 Metals(Japan Association for Working EnvironmentalMeasurement, 20 September 2005)

Atmosphere

111

Fig. 4.12.1 Mass spectrum from qualification of coal fly ash (m/z: 195-223)

Table 4.12.1 Quantitation results on coal fly ash (NIST 1633-b) (units: µg/g)

4.12 Analysis of Inorganic Components in Fly Ash (2) - ICP/MS

Element Quantitation value Certified value

( ) indicates a reference value.

112

5.1 Analysis of PCBs in Insulating Oil - GC

■ ExplanationThirty years have passed since the ban on PCB manufacturing,importing, or use in unsealed systems. Waste PCBs fromtransformers that reach the end of their service life must bestored as industrial waste. The analysis of PCBs is gainingincreasing prominence, as their long-term storage leads toconcerns about environmental contamination by PCBs due tothe loss or leakage of containers. Packed columns are mainlyused for quantitation of PCBs. However, discrepancies occur inPCB separation due to the column used and the analysistakes a long time. This section introduces PCB separationusing a non-polar wide-bore column. Fig. 5.1.1 and 5.1.2show the chromatograms for insulating oil spiked with 0.5µg/L and 3 µg/L PCB after pretreatment according to theJEAC* 1201 method. Good separation was achieved, despitethe many impurity components in the insulating oil. * JEAC: Japan Electric Association

5. Industrial Waste

■ Analtytical ConditionsInstrumentColumnColumn TemperatureCarrier GasDetectionMakeup GasInjection Inlet TemperatureInjection MethodInjection Volume

: GC-17A, ECD-17, AOC-20iRtx-1 (30 m × 0.53 mm I.D. df=1.0 µm)

: 210˚C: N2, 15 mL/min: ECD, Detector Temperature: 280˚C : N2, 50 mL/min: 250˚C : Direct Injection: 2 µL

Fig. 5.1.1 Chromatogram of PCB in insulating oil using Rtx-1 wide-bore column (insulating oil spiked with 3 µg/L PCB)

Fig. 5.1.2 Chromatogram of PCB in insulating oil using Rtx-1 wide-bore column (insulating oil spiked with 0.5 µg/L PCB)

0.0

1

23

4 5

67 8

9

1011

1213

14+1516

1718

19

20+unknown

21 2223 24 25 26

2.5 5.0 7.5 10.0 12.5 15.0 17.5 min

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

3.0µV(×1,000)

0.0 2.5

1

2

3

4

5

678

9

10

11

1213

14

15 16

17

1819

20 21

22 2324 25

26

5.0 7.5 10.0 12.5 15.0 17.5 min

0.00

0.25

0.50

0.75

1.00

1.25

1.50

1.75

2.00

2.25

µV(×10,000)

Industrial Waste

113

5.2 Measurement of Metals in Industrial Waste - AA

■ ExplanationMetals in industrial waste must be measured according tothe methods described in the Environment Agency OrdinanceDetection Methods for Metals in Industrial Waste (OrdinanceNo. 13, 17 February 1973). Table 5.2.1 lists the metal measurementsintroduced in this section.However, industrial waste also contains substances that mustbe subjected to content measurement, such as organic sludge, acidwaste, and waste alkaline. These measurements were made by AAanalysis on the solution obtained from the elution methodshown in Fig. 5.2.1. The target metals for the measurementsare cadmium, lead, hexavalent chromium, arsenic, selenium,and mercury (measured by the reduction vapor method). Forocean dumping, copper and zinc are added. Table 5.2.2 listssome of the evaluation criteria.

■ Details of the Elution MethodPulverize the sample, if necessary. Use standard sieves No. 32and No. 4 to obtain sample from 0.5 mm to 5 mm particle size.The elution method is divided into three classes, as shown inTable 5.2.1. The elution solvents were made as follows: forlandfill disposal, hydrochloric acid was added to purifiedwater to achieve a pH from 5.8 to 6.3; for dumping at sea and sea-based solid waste disposal, sodium hydroxide was added topure water to achieve a pH from 7.8 to 8.3. For wastesequivalent to classes a and b in Table 5.2.1, the sample andsolvent are mixed at 10 % (w/v) and elution is conducted toobtain at least 500 mL of this mixture. For wastes equivalent toclass c in Table 5.2.1, sample and solvent are mixed to obtain 3% proportion (w/v) of solids in the mixture and elution isconducted to obtain at least 500 mL of this mixture.For elution, the sample is first shaken continuously for 6 hours ina shaker at room temperature and atmospheric pressure. Thesample solution obtained is filtered through glass fiber filterpaper and then analyzed. If filtering is difficult, centrifuge thesample at 3000 rpm for 20 minutes and measure thesupernatant.

■ Measurement of Chromium by AAAs an example of AA analysis, Fig. 5.2.2 shows the analysis ofchromium in fly ash. Table 5.2.3 shows the majormeasurement conditions. After filtering, the sample is diluted 20times before analysis by the calibration curve method.

Table 5.2.1. Classes of elution method

Fig. 5.2.1 Overview of the elution method

Table 5.2.2 Some evaluation criteria for industrial waste containing metals

Fig. 5.2.2. Measurement results for chromium

Table 5.2.3 Measurement conditions for chromium

Pulverization

Sieving (0.5 mm to 5 mm)

Sample weighing

Elution solvent (landfill disposal : pH 5.8 to 6.3 ;dumping at sea and sea-based solid waste disposal : pH from 7.8 to 8.3)

Shaking(6 hours at shaking speed: 200 shakes/minute, amplitude 4 cm to 5 cm)

Filtering (1 µm pore size glass fiber filter paper)(centrifuging in some cases)

Measurement

Processed products from disposal of burnt residues, sludge, mine tailings and dust (excluding burnt residues, sludge and dust), mine tailings

Landfill disposal(excluding sea-basedsolid waste disposal)

a

b

c

Sea-based solidwaste disposal

Burnt residues, sludge, dust, mine tailings Processed products (limited to sludge) from disposal of dust

Burnt residues, inorganic sludge (excluding water-soluble sludge and sludge related to the testing of organochlorines), dust

Sea-basedsolid waste

Dumping at sea

Dumping at sea

Burnt residues, sludge, mine tailings, dust, processedproducts from disposal of these industrial wastes

Incinerated sludge, mine tailings

Class Disposal method Applicable wastes

0.005 mg/L0.3 mg/L0.3 mg/L1.5 mg/L0.3 mg/L0.3 mg/L

0.005 mg/L0.01 mg/L0.01 mg/L0.05 mg/L0.01 mg/L0.01 mg/L0.14 mg/L

0.8 mg/L

Disposal method

Disposed wastes

Controlled item

Mercury and its compounds

Cadmium and its compounds

Lead and its compounds

Compounds of hexavalent chromium

Arsenic and its compounds

Selenium and its compounds

Copper and its compounds

Zinc and its compounds

Landfill

Burnt residues, dust, sludge, mine tailings

Ocean dumping

Non-water-soluble inorganic sludge

Calibration curve (Calibration curve No. 01) Conc Abs

(ppb)

1.0000 0.1042

2.0000 0.2015

3.0000 0.2922

Abs = - 0.00338Conc ^ 2 + 0.1075Conc + 0

r = 1.0000

0.000 1.000 2.000 3.000Conc (ppb)

0.000

0.100

0.200

0.300Abs

: STD AverageSet concentration Absorbance

Set concentration Absorbance

Set concentration Absorbance

1.0000 0.1042

: STD Average

2.0000 0.2015

: STD Average

3.0000 0.2922

Fly ash : UNK AverageConcentration Absorbance Dilution

Actualconcentration Conc. units

1.8461 0.1870 20.00 36.9220 ppb

wavelengthslitmeasurement mode

357.9 nm0.5 nmBGC – D2

Temperature program (tube: pyrolized graphite tube)

Stage

12345

* 67

150350900900900

23002500

20101010

322


0.100.101.001.000.000.001.00

Temp. (°C) Time (s) Heating mode Ar gas flow rate (L/min.)

* Stage 6 is the atomization stage.

114

5.3 Screening of Waste Plastic Material using Horizontal ATR (1) - FTIR

■ ExplanationA wide range of plastic materials is used in automobiles,household appliances and different kinds of containers tothe extent that we have arrived at an era where recyclingshould become compulsory. The first important step inrecycling plastics is the task of screening for separationpurposes of the different types of plastics that have beencollected. Here, the requirements are (1) instantaneousdistinction, (2) measuring regardless of shape, and (3)measuring online. At the moment, the FTIR has troublefulfilling all three requirements, however this sectionintroduces a horizontal ATR method using diamond prismwith which the FTIR measures objects regardless of shapecomparatively well – especially solid objects.

■ Device OutlineFigure 5.3.1 shows a diagram of the instrument. On the topsection of the instrument there is a stainless steel platesecured with a diamond prism implanted its central section.There are two types of plate available, one with a single-reflector (diameter of 1mm) prism and the other with a multi-reflector (diameter of 3 mm) prism, and sample holding bypressure adjustment can also be installed. Furthermore, on theleft and right sides of the instrument there are purge pipefittings that can be fitted into the sample chamber wall, sothat even if the sample chamber lid is open, measuring canstill be performed without any affect on the atmosphere in thechamber.

■ Measuring Conditions

Fig. 5.3.1 External view of instrument

DecompositionAccumulationApodize FunctionDetector

: 8 cm-1

: 100: Happ-Genzel: DLATGS

Industrial Waste

115

5.3 Screening of Waste Plastic Material using Horizontal ATR (2) - FTIR

■ Measuring ExamplesFigures 5.3.2 to 5.3.5 show the spectra profiles of polystyrene(PS), polyethylene (PE), polypropylene (PP), and acrylonitrilebutadiene styrene resin. All of these figures show results for

plate-shaped samples, but the FTIR can be used to measurequite hard objects like pellets and powder samples.

Fig. 5.3.2 PS spectrum (1/cm)

0.2

ABS

PS

0.0

2500 1000 7004000

Fig. 5.3.3 PE spectrum (1/cm)

PE

2500 1000 7004000

0.1

ABS

0.0

Fig. 5.3.4 PP spectrum (1/cm)

PP

0.1

2500 1000 7004000

ABS

0.0

Fig. 5.3.5 ABS spectrum (1/cm)

2500 1000 7004000

0.05

ABS

ABS

0.0

116

5.4 Analysis of Inorganic Components in Fly Ash - ICP/MS


: ICPM-8500

: 1.2 kW: 7 L/min: 1.5 L/min: 0.62 L/min


■ ExplanationAfter incineration and compacting, municipal waste isdisposed of as specially controlled municipal waste inlandfill. The metal content of fly ash must be measured todetermine the amount of metal leaching into theenvironment. The amount of Cd, Hg, Pb, Cr6+, As, Cu, andZn leaching into the environment is controlled by law. Such industrial waste often contains high concentrations ofinterfering elements, which makes measurement difficult.ICPM-8500 offers highly sensitive measurements, relativelyunaffected by the interfering elements. This sectionintroduces the analysis of fly ash from municipal waste.Quantitation was conducted using the calibration curvemethod. Table 5.4.1 shows the quantitation results expressedas solid concentrations.

■ SampleBCR-176 Municipal Waste Fly Ash Standard(Supplied by Osaka City Institute of Public Health andEnvironmental Sciences.)

■ PretreatmentWeigh approx. 0.5 g sample into a fluororesin beaker. Add10 mL nitric acid and 20 mL hydrochloric acid. Cover thebeaker with a fluororesin watchglass. Heat on a hot plate at120˚C for approximately 1 hour to conduct thermalextraction. After cooling, make up to 100 mL with ultrapurewater. Filter through 5B (medium) filter paper and dilute thefiltrate 500 times with pure water to prepare the analysissample. Spike with 50 ppb Y and Tl internal standards.

■ Calibration Curve SampleMix AA-grade standard solution (1000 ppm) and thendilute as appropriate with ultrapure water. Spike with 50ppb Y and Tl internal standard elements and add 1 % nitricacid.

References(1) Test Methods for Metals in Industrial Waste;

Environment Agency Ordinance, 17 February 1973,Ordinance 87 partially revised 2005, Ordinance 16partially revised 1998

(2) Wastewater Test Methods, Japan Sewage WorksAssociation, August 1997

(3) JIS K0102-1998 Testing Methods for IndustrialWastewater

Certified valueElement Measured value

Table 5.4.1 Quantitation results on fly ash (BCR-176) (units: mg/kg)

Industrial Waste

117

5.5 Determination of Asbestos in Admixture for Mortar - TA

■ ExplanationDifferential thermogravimetry (D-TG) is an effectivemethod for measuring serpentinite in mixed cementmaterials and is listed in the July 2004 Ministry of Health,Labor and Welfare notification Prevention of AsbestosExposure from Mortar Admixtures Containing Serpentine.To improve spreadability, plasterers use mixed cementmaterials containing pulverized serpentinite, the majorconstituent of serpentinite, include chrysotile that is anasbestos mineral and antigorite and lizardite that are non-asbestos minerals. So, when using serpentine, it isimportant to confirm whether or not it contains chrysotile.After identifying serpentinite by X-ray diffractometry, D-TGanalysis must be conducted to confirm whether it containschrysotile. First, conduct X-ray diffractometry to confirm that the rockis serpentinite. If it is confirmed as serpentinite, the type ofserpentine must be identified. However, chrysotile,antigorite, and lizardite have a very similar chemicalcomposition and crystal structure. All three types producelarge peaks near 12˚ and 24˚ in the X-ray diffractionpattern, but their differences are expressed as small peaksaround 35˚ to 36˚. However, the peak intensity indicatingchrysotile is weaker than the peaks for antigorite andlizardite. If the minerals are mixed, it may be impossible toconfirm the chrysotile (asbestos) even if it is present. D-TGanalysis must be conducted to confirm the presence ofchrysotile. The chemical composition of all serpentineminerals is Mg3Si2O5(OH)4. The (OH)4 is equivalent to thewater of crystallization, which is driven off between 600˚Cand 800˚C. The dehydration temperature is lowest forlizardite at 630˚C to 680˚C, followed by chrysotile at 650˚Cto 700˚C, and highest for antigorite at 750˚C to 800˚C. Bymeasuring this dehydration with a thermogravimeter, it ispossible to confirm whether chrysotile (asbestos) is presentfrom the differences in peak temperature on the differential

thermogravimetric (D-TG) curve. (Differential thermogravimetric(D-TG) analysis is conducted by differentiating the TG curve thatshows thermogravimetric changes.)

■ Measurement of Chrysotile and AntigoriteApproximately 20 mg pulverized sample was measured at20˚C/min heating rate. Changes appear due to dehydrationof the respective waters of crystallization. The peaktemperatures on the D-TG curves are 680˚C for chrysotileand 760˚C for antigorite. Differential thermogravimetric (D-TG) analysis in theNotification refers to the D-TG curves resulting fromdifferentiation of the thermogravimetric changes.

■ D-TG Measurement of Admixtures for MortarDifferential thermogravimetric (D-TG) analysis wasconducted on admixtures for mortar for which serpentinepeaks were detected by X-ray diffractometry. Each sampleexhibited peaks in the D-TG curve around 650˚C and 770˚Cto 780˚C, confirming the presence of chrysotile andantigorite. One admixture sample was shown to contain ahigh proportion of chrysotile. Quantitation of eachcomponent was possible by measuring the peak areas.

0.0 200.0 400.0 600.0 800.0Temp[˚C]

-1.00

-0.50

0.00

0.50

1.00

mg/minDrTGA

669.0˚C

648.3˚C

652.6˚C

766.9˚C

647.7˚C

Admixture for mortar A

Admixture for mortar B

Admixture for mortar C

Admixture for mortar D

775.6˚C

777.0˚C

775.6˚C

777.0˚C

Test sample

Powdered

X-ray diffraction analysis

Confirmation of serpentine peaks

D-TG Analysis

Confirmation of chrysotile, antigorite, and lizardite

Calculation of chrysotile content

Fig. 5.5.1 Determination of chrysolite in serpentine rock Fig. 5.5.3 Measurement of admixtures for mortar

0.0 200.0 400.0 600.0 800.0Temp[˚C]

-200.0

-100.0

0.0

100.0

200.0

TGA%

-2.00

-1.00

mg/minDrTGA

765.0˚C

677.0˚C

Chrysotile

Antigorite

TG

D-TG

TG

D-TG

Fig. 5.5.2 Measurement of chrysotile and antigorite

118

5.6 Analysis of Asbestos - XRD

■ Analytical Conditions (chrysotile)ItemX-ray Conditions

Monochromator

Slit Conditions

Scan Rate

Scan Range

Sample Rotational Speed

QuantitationCuKα Line40 kV, 40 mAGraphite MonochromatorDS : 1, SS : 1˚RS : 0.3 mm2˚/min0.02˚ step2 θ : 5˚~70˚

60 RPM

■ ExplanationIn Japan, new regulations were introduced to preventdamage from asbestos in July 2005. Of the buildingmaterials subject to these regulations, quantitation using thestandard addition method or the internal standard method byX-ray diffractometry is possible, if the material contains 5 %or more asbestos by weight. However, quantitation is notpossible on some materials containing less than 5 %asbestos. In these cases, pretreatment with formic acid isconducted to dissolve only the matrix components in thesample and quantitation is then conducted with an X-raydiffractometer using the base standard absorption correctionmethod. Fig. 5.6.1 shows the diffraction patterns for different types ofasbestos. Fig. 5.6.2 shows an example of the qualitativeanalysis of chrysotile in slate sheets (search results). Fig.5.6.3 shows an example of the measurement of slatematerials.

QuantitationCuKα Line40 kV, 40 mAGraphite MonochromatorDS : 1, SS : 1˚RS : 0.3 mm5˚/min0.02˚ step2 θ : 11˚~13˚2 θ : 42˚~44˚30 RPM

Chrysotile standard

Amosite standard

Crocidolite standard

Inte

nsity

(C

PS

)

8-28 (degrees)

[Group name] Environmental analysis (qualification) [Data name] Slate [Date/Time] 05-08-22 18 : 47 : 43

Chrysotile

Peak data

Profile

Registered dataResidual peak

Card data

No. Card Chemical formula Mineral name Density Spatial group

Fig. 5.6.1 Diffraction patterns for different types of asbestos

Fig. 5.6.3 Measurement of slate materials (chrysotile)

Fig. 5.6.2 Search Results on Slate Sheets (Chrysotile)

Industrial Waste

119

5.7 X-ray Fluorescence Spectrometric Analysis of Industrial Waste (Sludge) - XRF

Fig. 5.7.1 Qualitative analysis of sludge

Table 5.7.1 Qualitative analysis value (%) of sludge

■ ExplanationIndustrial wastes like sludge and mud have their elementsanalyzed so that they can be classified for burial,management or reuse. Easy, fast and thorough fluorescentx-raying is the optimum form of analysis for this work. Themeasuring method employed is qualitative and quantitativeanalysis. With this method, qualitative analysis isconducted, followed by quantitative analysis of the detectedelements or the intensity of that fluorescent x-ray with FPmethod. Standard samples are not necessary, so this methodis extremely useful when the types of analysis samples arenumerous and the marketed standard samples are few. Fig.5.7.1 and Table 5.7.1 show qualitative and quantitativeanalysis results of sludge as analysis examples of industrialwaste.

■ PretreatmentGrinding Conditions

InstrumentContainerTime

: Shaker Mill T1-100: Tungsten Carbide : 3 min

DevicePressureTimeRing

: Briquet Machine MP-35: 30 t: 30 sec: Vinyl Chloride

■ Analtytical ConditionsInstrument

X-ray TubeTube VoltageTube AmpereSpectrometer Crystals

Scanning Speed

: Sequential X-ray FluorescenceSpectrometer XRF-1700

: 4kW, Be Thin Window, Rh Target: 40kV: 95mA: LiF, Ge, PET, TAP, SX-48,

SX-58N, SX-76, SX-14: 8 ˚, 4 ˚, 2 ˚/min

Pressurized Design Conditions

CO2

60.73

N2O5

9.99

Na2O

0.17

MgO

0.85

Al2O3

6.97

SiO2

8.89

P2O5

5.72

SO3

2.12

Cl

0.064

K2O

0.31

CaO

2.81

TiO2

0.16

Cr2O3

0.012

MnO

0.038

Fe2O3

0.90

NiO

0.004

CuO

0.018

ZnO

0.055

Br

0.002

Rb2O

0.001

SrO

0.019

Y2O3

0.000

BaO

0.18

PbO

0.002

120

6. Others

Weigh soil (50 g 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 4 hr using magnetic stirrer.

Allow to stand for 30 min, then filter supernatant.

Analyze headspace gases over filtered liquid.

Fig. 6.1.1 Example of pretreatment in analysis for residual MTBE in soil

min

Intensity

0 10 20 30

-1000

100200300400500600700800900

MT

BE

Tol

EB

m,p

-Xy

o-X

y

Fig. 6.1.2 Chromatogram of water extracted from gasoline-added soil

6.1 Easy Analysis of Residual MTBE in Soil (HS Method) - GC

■ ExplanationMTBE (Methyl-t-butyl ether) is a component added mainlyto high-octane gasoline to increase the octane number. InJapan, a decision was finalized by the major retailers ofpetroleum products in the summer of 2001 to prohibitselling high-octane gasoline containing MTBE (which issuspected of being carcinogenic) because discharges ofsuch fuel would lead to the fear of soil and ground waterpollution. The normal methods for measuring residualMTBE in environment water and soil are the headspaceGC/MS and purge & trap GC/MS ones; however, forscreening purpose, GC-FID analysis seems to be often usedinstead.

References(1) Environment Agency bulletin No. 46, Environment

Standards Related to Soil Pollution, 23.8.91Amendments: 1993 environment bulletin No. 19, 1994environment bulletin No. 25, 1995 environment bulletinNo. 19 concerning low molecular weight hydrocarbonanalysis

(2) Shimadzu Application News No. G208


Column Temperature

Injection Inlet TemperatureDetector TemperatureCarrier GasInjection MethodHeadspace ThermostattingInjection Time

: GC-2010 + HS40: DB-VRX (60 m × 0.25 mm I.D.

df = 1.4 µm): 35˚C (13 min) -13˚C/min -185˚C

(13 min) -15˚C/min -255˚C: 150˚C: 250˚C (FID): He 230 kPa (2.2 mL/min): Split (1:8): 80˚C, 30 min: 0.1 min

121

10 g of fish

GC/MS

Analyte: 2 mL

Column chromatography (Florisil)

Propylation (Grignard reagent: PrMgBr)

Column chromatography (cation, anion exchange resin)

Extraction (ethyl acetate: hexane 3:2)

Extraction (1N hydrochloric acid methanolic solution)

1 L seawater

GC/MS

Analyte: 2 mL

Propylation (Grignard agent: PrMgBr)

Extraction (ethyl acetate: hexane 3:2)

Fig. 6.2.1 Example of extraction method for organic tin

Fig. 6.2.2 TBT mass spectrum Fig. 6.2.3 TPT mass spectrum

6.2 Analysis of Organic Tin in Seawater and Fish (1) - GC/MS, GC

■ ExplanationTBT (Tributyl Tin) and TPT (Triphenyl Tin), etc., havebeen widely used as antifouling agents on the hulls of shipsand on fishing nets to prevent adhesion of shellfish andseaweed. In 1997, Japan halted the production of paintcontaining TBT, but some other nations are still using TBT,which is a cause of seawater and marine life pollution.Also, TBT is suspected of having an endocrine disruptingeffect. This data introduces analysis examples of the highlyqualitatively accurate GC/MS method that can usedeuterated (d labeling) compounds for internal standardsubstances and the conventional GC-FPD analyzingmethod.

Reference(1) Shimadzu Application News No. M182(2) Shimadzu Application News No. G190

■ Analytical Conditions (GC/MS)GCColumn

Column Temperature

Injection Inlet TemperatureCarrier GasInjection MethodInterface TemperatureMSScanIonizationScan RangeSIM

d27TBTTetra-BTTpeTd 15TPTTPT

: DB-1 (30 m × 0.32 mm I.D. df = 0.25 µm)

: 50˚C (2 min) -20˚C/min -140˚C -7˚C/min -220˚C -15˚C/min -310˚C

: 280˚C: He 40 kPa : Splitless (2 min): 300˚C

: EI: m/z 35 - 450

Selected Ion (m/z): 295, 293, 316 : 277, 275, 291: 291, 289: 303, 305: 366, 364: 351, 346

Others

122

■ Analytical Conditions (GC)

Sea Bream

0.436 µ/g

0.014 µ/g

0.782 µ/g

0.010 µ/g

0.173 µ/L

0.019 µ/L

0.068 µ/L

0.078 µ/L

Compound

TBT

TPT

Sea Bass K Harbor W Harbor

0 5 10 15 20 25 min

5

mV

10

123 4

5

6

8

9

7

10

1112

0 5 10 15 20 25min

mV

0

2

1 23 45

6

7

8

910

1112

4

6

Fig. 6.2.4 SIM chromatograms for standard sample Fig. 6.2.5 SIM chromatograms for TBT in fish (sea bass)

Table 6.2.1 Quantitative results for tin in fish and seawater

Fig. 6.2.6 Chromatogram of standard solution

Fig. 6.2.7 Chromatogram of fish (sea bass) extraction solution

Compounds

1.Monobutyl Tin

2.Dibutyl Tin(d18)

3.Dibutyl Tin

4.Tributyl Tin(d27)

5.Tributyl Tin(TBT)

6.Tetrabutyl Tin(TeBT)

7.Monophenyl Tin

8.Tripentyl Tin(TPeT)

9.Diphenyl Tin(d10)

10.Diphenyl Tin

11.Triphenyl Tin(d15)

12.Triphenyl Tin(TPT)

Compounds

1.Monobutyl Tin

2.Dibutyl Tin(d18)

3.Dibutyl Tin

4.Tributyl Tin(d27)

5.Tributyl Tin(TBT)

6.Tetrabutyl Tin(TeBT)

7.Monophenyl Tin

8.Tripentyl Tin(TPeT)

9.Diphenyl Tin(d10)

10.Diphenyl Tin

11.Triphenyl Tin(d15)

12.Triphenyl Tin(TPT)

6.2 Analysis of Organic Tin in Seawater and Fish (2) - GC/MS, GC

InstrumentColumn

Column Temperature

: GC-17A (FPD): DB-5 (30 m × 0.25 mm I.D.

df = 0.25 µm): 60˚C (1 min) -20˚C/min -140˚C

-7˚C/min -280˚C

Injection Inlet TemperatureCarrier Gas

Injection MethodInjection Volume

: 290˚C: He 350 kPa (1 min)

-150 kPa (2.4 mL/min): High-Pressure Injection, Splitless: 3 µL

ID : 6 mass number : 277.00type : Targetcomponent : TBT

retention time : 10.788area : 44583concentration : 1.021ppm

mass number area intensity ratio1 291.00 18581 42

123

6.3 Analysis of Volatile Organic Compounds (VOCs) in Soil (HS, P/T Method) (1) - GC/MS

■ ExplanationThe headspace method and purge trap method are used foranalysis of volatile organic compounds in soil. Theheadspace method features ease of use, provides goodreproducibility, can accommodate an auto sampler, andcarry over (conforming pollutant level of device caused byconcentration level of elements) is minimal. The purge trapmethod allows analysis of low-concentrate samples at highsensitivity as samples can be concentrated using acollecting agent, which provides excellent sensitivity of 10to 100 times more than that of the headspace method.

References(1) Drinking Water Test Method & Explanation

(2001 Edition) Japan Water Works Association(2) Environmental Water Analysis Manual, Environmental

Science Research Group volume(3) New Wastewater Standards and Other Analysis

Methods, Environmental Science Research Groupvolume

(4) Concerning additional items for environment standardrelated to soil pollution(Verdict) Central Environment Think Tank January14th, 1994

■ PretreatmentCreation of Sample

Gravel and pieces of wood exceeding a granulardiameter of 5 mm are removed from collected soil.

Sample Solution Preparation50 g of sample and 500 mL of solvent (purified water:water without VOCs) are placed in a 500 mL conicalflask with threaded inlet and agitator placed inside, andthe flask sealed immediately.

Solving OutThe prepared sample is kept at room temperature andatmosphere (20˚C and 1 atmosphere) while beingcontinually stirred for 4 hours using a magnetic stirrer.

Creation of Test SolutionWhen the above operations are completed, let thesample solution stand for 10 to 30 minutes, then pass itthrough a membrane filter with perforation diameter of0.45 µm to make the measuring sample solution.

■ Analtytical ConditionsHead Space Method

Head Space Sampler HS-40Sample VolumeSample TemperatureHeating TimeNeedle TemperatureLine TemperaturePressurization TimeInjection Time

: 10 mL+NaCl 3g: 60˚C: 30 min: 120˚C: 150˚C: 2 min: 0.20 min

Shimadzu GCMS-QP5050A

Carrier GasColumnColumn Temperature

: He 120 kPa: DB-624 (60 m × 0.32 mm I.D. df=1.8 µm): 40˚C (2 min)-10˚C/min -200˚C (2 min)

Purge Trap MethodTEKMAR-DOHMANN LSC3000

Sample VolumeAdsorption TubePurge TimeDry Purge TimePurge Flow RateDesorption TimeInjectionBakingTransfer

: 5 mL: G-2 (Tenax-Silica gel): 5 min (room temp): 2 min: 30 mL/min: 3 min (200˚C): 2 min (200˚C): 220˚C (30 min): 150˚C

Shimadzu GCMS-QP5050ACarrier GasColumn

Column Temperature

: He 120 kPa: DB-624 (60 m × 0.32 mm I.D. df=1.8 µm)

: 40˚C (5 min) -4˚C/min-80˚C-6˚C/min-140˚C-8˚C/min-180˚C-40˚C/min-200˚C (2 min)

Others

124

6.3 Analysis of Volatile Organic Compounds (VOCs) in Soil (HS, P/T Method) (2) - GC/MS

6 8 10 12 14 16 18 20 22 24 26 (min)

12

3 4

5

6

TIC 89488

7

8

9

101112

13

14

15

17

16

18

19

20

2122

23

Fig. 6.3.1 SIM chromatograms (headspace method) for sample with 23standard compounds (1µg/L) added to soil

TIC

Toluene

Tetrachloroethylene

2000000

6 8 10 12 14 16 18 20 22 24 26 28 (min)

Fig. 6.3.2 SIM chromatogram of soil (purge . trap method)

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20

21

22

23

ID

1,1-Dichloroethene

Dichloromethane

trans-1,2-Dichloroethene

cis-1,2-Dichloroethene

Chloroform


Tetrachloromethane

Benzene

1,2-Dichloroethane

Trichloroethene

1,2-Dichloropropane

Bromodichloromethane

cis-1,3-Dichloropropene

Toluene

trans-1,3-Dichloropropene

1,1,2-Trichloroethene

Tetrachloroethene

Dibromochloromethane

m,p-Xylene

o-Xylene

Bromoform

p-Bromofluorobenzene(IS)

p-Dichlorobenzene

Name

96,61

84,86

96,61

96,61

83,85

97,99

117,119

78,77

62,64

130,132

63,62

83,85

75,110

92,91

75,110

97,99

166,164

129,127

106,91

106,91

173,175

174,176

146,148

SIMSelected Ions

Table 6.3.1 SIM selected ions

125

Others

6.4 Analysis of Metals in Soil - AA

■ ExplanationThe Soil Contamination Countermeasures Law proclaimed in2002 lists as specified toxic substances 9 heavy metals thatcan linger for long periods at high concentrations in the soiland 25 elution standard items set in the Environmental Quality

Standards for Soil from the viewpoint of ingestinggroundwater. This section presents examples of the analysis oftoxic metals in soil using the AA, ICP, and ICP/MS methodsthat are widely used for the analysis of inorganic elements.

■ Sample Preparation(1) Sample Preparation for Elution Standard(Ministry of the Environment Notification No. 18, dated 6 March 2003)Target components: alkyl mercury, mercury, cadmium, lead,hexavalent chromium, arsenic, selenium, cyanide, boronStore the collected soil sample in a glass container or othercontainer that causes no adsorption or elution of the targetsubstances. After air drying and passing through a non-metallic 2 mm sieve, take at least 50 g of the sample. Usehydrochloric acid adjusted to pH 5.8 to 6.3 as the solvent.Mix the solvent and sample in a 10:1 liquid/solid ratio andthen shake at approximately 200 shakes/min (amplitude 4 to5 cm) for 6 hours at room temperature for sample elution.Centrifuge for 20 minutes at 3000 rpm and filter through a0.45 mm membrane filter to produce the sample.(2) Sample Preparation for Soil Content Standard(Ministry of the Environment Notification No. 19, dated 6 March 2003)Target components: Hg, Cd, Pb, Cr6+, As, Se, B, FStore the collected soil sample in a polyethylene container orother container that causes no adsorption or elution of thetarget substances. After air drying and passing through anon-metallic 2 mm sieve, take at least 6 g of the sample. Use1 mol/L hydrochloric acid as the solvent. (However, for Cr6+

use 5 mM Na2CO3 + 10 mM NaHCO3 alkaline buffersolution) Mix the solvent and sample in a 100:3 liquid/solidratio and then shake at approximately 200 shakes/min(amplitude 4 to 5 cm) for 2 hours at room temperature forsample elution. Filter through a 0.45 mm membrane filter toproduce the sample.

■ Measurement ResultsThree samples (JSAC 0411 and SRM 2711 soil standardsamples and the NIES No. 2 pond sediment standardsample) were measured using the soil content standardmethod. Table 6.4.2 shows the content in the standardsamples of the metals that are the main target componentsof the Soil Contamination Countermeasures Law. Tables6.4.3 and 6.4.4 show the measured results for Cd and Pb,respectively (units: mg/kg).

■ ConclusionThe sample preparation for the soil content standard involveselution in 1 mol/L hydrochloric acid. The sample does notnormally fully dissolve under these conditions.Consequently, when standard samples are measured, theresults are generally lower than the indicated content values.

Table 6.4.2 Metal content of standard samples (partial)

Table 6.4.3 Measured results for Cd

Table 6.4.4 Measured results for Pb

Table 6.4.1 Target elements with their standards and measurement methods

Cd

Cr6+

Total HgSe

Pb

As

B

Measurement methodFAA,FLAA,ICP-AES,ICP/MSUV,FAA,FLAAICP-AES,ICP/MSReduction vapor AAHydride generation FAA, ICP-AESFAA,FLAA,ICP-AES,ICP/MSUV,Hydride generation FAA, ICP-AES

UV,ICP-AES,ICP/MS

Soil content standard (mg/kg)

<150

<250

<15<150

<150

<150

<4000

Second elution standard (mg/L)

<0.3

<1.5

<0.005<0.3

<0.3

<0.3

<30

Soil elution standard (mg/L)

<0.01

<0.05

<0.0005<0.01

<0.01

<0.01

<1

As

Cd

Cr

Pb

Se

JSAC0411

11.3±0.5

0.274±0.02

23.5±1.8

18.9±2.6

1.32±0.27

SRM2711

105±8

41.7±0.25

47

1162±31

1.52±0.14

NIES No.2

12

0.82

75

105

N/A

Pb(mg/kg)

AA

ICP

ICP/MS

JSAC041

10.5

11.8

12.0

SRM2711

1046

1070

1040

NIES No.2

67.6

67.5

69.2

Cd(mg/kg)

AA

ICP

ICP/MS

JSAC041

0.2

0.2

0.2

SRM2711

30.2

36.5

37.4

NIES No.2

0.6

0.6

0.6

* FAA indicates flame atomic absorption spectrometry. FLAA indicates flameless atomic absorption spectrometry.

126

6.5 Analysis of Chromium in Soil using Atomic Absorption Spectrometry - AA

■ ExplanationThe Soil Contamination Countermeasures Law implementedin Japan in 2003 defines soil elution standards and soil contentstandards for metals such as cadmium and lead and also forhexavalent chromium. This section descries the analysis ofchromium in a commercial soil standard sample (JSAC 0411Brown forest soil, Japan Society for Analytical Chemistry).

■ Sample PreparationFig. 6.5.1 and Fig. 6.5.2 show an outline of the samplepreparation method for hexavalent chromium according tothe soil elution standard (Ministry of the EnvironmentNotification No. 18, dated 6 March 2003) and according tothe soil content standard (Ministry of the EnvironmentNotification No. 19, dated 6 March 2003), respectively.

■ Analysis MethodThe sample was measured according to the analysis methodfor hexavalent chromium described in item 65.2 of JISK0102-1998 Testing Methods for Industrial Waste Water.JIS K0102-1998 defines five methods for the analysis ofhexavalent chromium, including diphenylcarbazideabsorption spectrometry and flame atomic absorptionspectrometry. However, this analysis was conducted byelectrothermal flame atomic absorption spectrometry("furnace AA"). Of these methods, only diphenylcarbazideabsorption spectrometry has selectivity for hexavalentchromium. Therefore, if the sample contains trivalentchromium, the analysis methods define iron coprecipitationto remove it. However, separation by iron coprecipitationwas not conducted during the analysis described here. Afixed volume of the sample solution was spiked with nitricacid and subjected to thermal decomposition beforeappropriate dilution to form the measurement sample. Tables6.5.2 and 6.5.3 list the major measurement conditions.

■ Measurement ResultsFig. 6.5.3 and Fig. 6.5.4 show parts of the peak profile from themeasurements and Table 6.5.4 lists the measurement results. Asthe elution concentration depends on the chemical species ofthe substance and the elution conditions, it is important toprocess the sample in compliance with the test method.

Sample preparation method

Concentration in sample (mg/L)

Liquid/solid ratio

Concentration in soil (mg/kg)

pH 6 extraction (elution test)

0.160

10/1

1.60

Alkaline extraction (content test)

0.0519

100/3

1.73

Abs0.500

0.250

0.000

Temperature Program

Tube TypeSample Injection VolumeInterference Inhibitor

Signal Processing

Drying: 150˚C, 20 s; 250˚C, 10 sAshing: 1000˚C, 25 s

Atomization: 2400˚C, 3 sCleaning: 2600˚C, 2 s

Pyrolized Graphite Tube5 µL

500 ppm Magnesium Nitrate, 5 µLArea

Analysis wavelength

Slid width

Current value

Ignition mode

357.9 nm

0.7 nm

10 mA

BGC-D2

Element

CdPbCrAsSeBeCuZn

Certified Value mg/kg (ppm)

4.25±0.4126±4

50.4±5.110.62±0.650.27±0.055.28±0.3515.3±1.366.8±2.7

10 ppb

5 ppb

2 ppb

Blank

Abs

0.500

0.250

0.000

Fig. 6.5.3 Peak profile of standard solution

Table 6.5.4 Measurement results for chromium in JSAC 0401 soil standard

Fig. 6.5.4 Peak profile of sample

Table 6.5.3 Atomization parameters

Table 6.5.2 Optics parameters

Fig. 6.5.2 Sample preparation method according to the soil content standard

Fig. 6.5.1 Sample preparation method according to the soil elution standard

Table 6.5.1 Certified values of metal element content of the soil standard sample (JSAC 0411 Brown Forest Soil) (partial)

127

6.6 Analysis of Non-agitated Soil Core Sample using Microscopic FTIR (1) - FTIR

■ ExplanationTo understand the existing form and distribution status ofinorganic compounds and organic compounds contained insoil, important information - such as knowledge of thefeatures attributable to the quality and formation of the soil inquestion - is needed. There are almost no examples of directsoil sampling using FTIR, but sampling of soil hardenedwith resin is possible. As a soil analysis method, the resinhardening method (1) is actively used to observe andanalyze micro structures and surface analysis, because soilsamples can be taken by core sampler and kept in a non-agitated state. Here, this section introduces a measuringexample of a sample prepared using this method.

Reference(1) Kenji Tamura, Sadao Nagatsuka, Hiroshi Ohba

Japan Soil Nutrient Society Magazine: 166-176 (1993)

■ PretreatmentThe sample used consisted of the A layer of black soil takenfrom an eulalia plain, and the pretreatment consisted of themethod depicted in reference material (1), which was

performed in the following way. The sample provided bycore sampler was wind dried, then hardened byimpregnation of a polyester-based resin. The sample wasthen cut to a suitable size, the surface polished, and used formeasuring. The prepared sample was set on the stage of aninfrared microscope, and measured by mapping employing areflective method for 5 × 5 mm range with aperture size 200 µmsquare.

■ ResultsFigures 6.6.1 and 6.6.2 show the silicic acid compoundfrom the spectra obtained in the measuring results. Bothfigures show absorption peculiarities for silicic acidcompound in the vicinity of 1100 cm-1.

■ Measuring Conditions

0.2

Abs

0.15

0.1

0.05

0.0

4000.0 2000.0 1000.0

Fig. 6.6.1 Inorganic compound spectrum (1)

ModeDecompositionAccumulationApodize FunctionDetectorData Processing Device

: Reflection: 8 cm-1

: 40: Happ-Genzel: MCT: Kramers-Kronig conv.

0.25

Abs

0.2

0.15

0.05

0.1

0.0

4000.0 2000.0 1000.0

Fig. 6.6.2 Inorganic compound spectrum (2)

Others

128

6.6 Analysis of Non-agitated Soil Core Sample using Microscopic FTIR (2) - FTIR

If the peak is targeted, and a three-dimensional measuringsurface is created from vertical axis values for the peak heightin a range of 800 to 1250 cm-1, the diagram in Fig. 6.6.3 can

be achieved. The protruding sections show the distributionof silicic acid compound.

Value (compensated height) range: 800 – 1250 1/cm

Fig. 6.6.3 Mapping diagram of soil core sample

129

6.7 Analysis of Inorganic Components in Soil (1) - ICP/MS

■ExplanationSoil samples often contain extremely complex interferingsubstances at high concentrations, which normally makesthe measurement of trace elements extremely difficult. Theanalysis method must achieve high sensitivity with littleinterference. This section describes the quantitation of soilsamples using Shimadzu ICPM-8500. Table 6.7.1 shows the quantitation results. The results aremultiplied by a dilution factor of 1000 to express them as aconcentration in a solid sample. Fig. 6.7.1 shows thecalibration curves.

■SamplesSoil standard samples NDG-2 (Field Subsoil) and NDG-7,8 (Rice Paddy Soil), produced by the Japanese Society ofSoil Science and Plant Nutrition.Supplied by Soil Chemistry Laboratory, Department ofPlant Production Chemistry, Tokyo University ofAgriculture

■PretreatmentWeigh 0.5 g soil sample into a fluororesin pressurizeddecomposition vessel. Add 5 mL high-purity nitric acid.Seal the vessel and heat at 170˚C for 3 hours. Allow tocool. Spike with internal standard elements and make up to100 mL with ultrapure water. Filter through 5B (medium)filter paper and dilute the filtrate 5 times with ultrapurewater to make the analysis sample.

■Calibration Curve SampleMix AA-grade standard solution (1000 ppm) and thendilute as appropriate with ultrapure water. Spike with 50ppb internal standard elements and add 1% nitric acid.

■Analytical ConditionsInstrumentPlasma Unit RF OutputCoolant Gas Flow Rate (Ar)Plasma Gas Flow Rate (Ar)Carrier Gas Flow Rate (Ar)Sample Introduction UnitNebulizerSample Intake RateChamberPlasma TorchSampling DepthSampling Interface

: ICPM-8500

: 1.2 kW: 7 L/min: 1.5 L/min: 0.62 L/min


References(1) Partial revision of Ordinances of Water Pollution

Prevention Law Related to Environmental Standards, 8 March 1993

(2) JIS K0102-1998 Testing Methods for Industrial Waste Water

Others

130

6.7 Analysis of Inorganic Components in Soil (2) - ICP/MS

Table 6.7.1 Quantitation results on soil solution (units: µg/g)

Fig. 6.7.1 Calibration curves

Sample name

ElementCertified

valueQuantitation

valueCertified

valueQuantitation

valueCertified

valueQuantitation

value

SDCorrelation

Units

SDCorrelation

Units

SDCorrelation

Units

SDCorrelation

Units

Coefficients

Coefficients

Coefficients

Coefficients

131

6.8 Analysis of Inorganic Components in Pond Sediment - ICP-AES

■ExplanationAnalysis was conducted using Shimadzu ICPS-7510 on a pondsediment standard. Table 6.8.1 shows the quantitation results.The values approximately match the certified values. Fig. 6.8.1shows the spectra profiles from the quantitation.

■SamplesNIES No. 2 pond sediment standard sample

■PretreatmentThermally decompose 0.2 g sample in nitric acid, hydrogenperoxide, and hydrofluoric acid. Allow to cool and transferinto a fluororesin beaker. Heat until it dries. Dissolve innitric acid and hydrochloric acid. Allow to cool and makeup to 100 mL with purified water to produce the analysissample.

■Analytical ConditionsInstrumentRF OutputCoolant Gas FlowRatePlasma Gas Flow RateCarrier Gas Flow RateSample Introduction ChamberPlasma TorchObservation Method

: ICPS-7510: 1.2 kW: 14 L/min: 1.2 L/min: 0.7 L/min: Coaxial Nebulizer: Cyclone Chamber: Standard Torch: Axial

Sample name: NIES No. 2/500 pond sediment standard sample Peak

Pond sediment

Pond sedimentPond sediment

Certified valueElement Quantitation results

( ) indicate reference values.

Table 6.8.1 Quantitation results on pond sediment standard sample (units: µg/g)

Fig. 6.8.1 Spectra profiles

Others

132

6.9 Analysis of Inorganic Components in Sewage Sludge (1) -ICP-AES, ICP/MS

■ExplanationSewage sludge from the sewage treatment process wasanalyzed with the Sequential Plasma Emission SpectrometerICPS-7510 and the Inductively Coupled Plasma MassSpectrometer ICPM-8500. Table 6.9.1 shows thequantitation results obtained by ICPM-8500 and ICPS-7510.Quantitation was conducted using the calibration curvemethod. The results are multiplied by a dilution factor toexpress them as a concentration in a solid sample.

■SampleSewage sludge from the sewage treatmentSupplied by Department of Civil and EnvironmentalEngineering, Faculty of Engineering, Iwate University.

■PretreatmentThe sample was pretreated by nitrohydrochloric acid (aquaregia) boiling method, the simplest method conforming tothe Waste Water Test Method. Weigh 10 g sludge sample(wet weight) into a fluororesin beaker. Add 15 mL nitricacid and 45 mL hydrochloric acid. Cover the beaker with afluororesin watchglass. Thermally decompose on a hotplate. When the contents reduce to approximately 10 mL,allow to cool and make up to 100 mL with ultrapure water.Filter through 5B (medium) filter paper and use the filtrateas the ICP-AES analysis sample. Dilute the filtrate 100times with ultrapure water to prepare the ICP/MS analysissample.

■Calibration Curve SampleMix AA-grade standard solution (1000 ppm) and then dilute asappropriate with ultrapure water. Spike with 1% nitric acid.

References(1) Waste Water Test Methods, Japan Sewage Works

Association, August 1997(2) JIS K0102-1998 Testing Methods for Industrial Wastewater

■Analytical Conditions

InstentPlasma Unit RF OutputCoolant Gas Flow Rate (Ar)Plasma Gas Flow Rate (Ar)Carrier Gas Flow Rate (Ar)Sample Introduction UnitNebulizerSample Intake RateChamberPlasma TorchSampling DepthSampling Interface

: ICPM-8500

: 1.2 kW: 7 L/min: 1.5 L/min: 0.62 L/min


InstrumentPlasma Unit RF OutputCoolant Gas Flow Rate (Ar)Plasma Gas Flow Rate (Ar)Carrier Gas Flow Rate (Ar)Sample Introduction UnitNebulizerChamberPlasma TorchObservation Method

: ICPS-7510

: 1.2 kW: 14 L/min: 1.2 L/min: 0.70 L/min

: Coaxial Nebulizer: Cyclone Chamber: Standard Torch: Longitudinal

ICP/MS

ICP-AES

133

6.9 Analysis of Inorganic Components in Sewage Sludge (2) -ICP-AES, ICP/MS

Table 6.9.1 Quantitation results on soil solution (units: µg/g)

Element Quantitation value Quantitation valueWavelength (nm)

Hydride generation method

Others

134

INDEXINDEX

1-Bromopropane 86

1-Chlorodecane 32

1,1-Dichloroethane 86,104

1,1-Dichloroethene 36,104,124

1,1-Dichloroethylene 31,87,90

1,1,1-Trichloroethane 31,36,87,90,104,124

1,1,1,2-Tetrachloroethane 86

1,1,2-Trichloroethane 31,36,87,90,104

1,1,2,2-Tetrachloroethane 86,104

1,2-Dibromoethane 104

1,2-Dichloroethane 31,36,87,90,103,104,105,124

1,2-Dichloropropane 31,36,37,87,90,104,124

1-(2-pyridyl) piperazine 94,95

1,2,3-Trichloropropane 26,27,33,86

1,2,4-Trichlorobenzene 104

1,2,4-Trimethylbenzene 104

1,3-Butadiene 86,103,104,105

1,3,5-Trimethylbenzene 104

1,4-Dichlorbenzene 37

1,4-Dioxane 29,30,31,34

1,4-Dioxane-d8 29,34

2-BPA (bromopropenamide) 43

2-Bromopropane 86

2-Butanone 96,98

2-Chlorophenol 28,33

2-Methylisoborneol 38,39,41

2-MIB 38,39,40,41

2,3-DBPA (dibromopropionamide) 43

2,4-Dichlorophenol 28,33

2,4-D (dichlorophenoxy acetic acid) 10,11,13,14

2,4-DNPH(Dinitrophenylhydrazine) 97,99,100

2,4-TDI 94

2,4,6-Trichlorophenol 28,33

2,6-Dichlorophenol 28,33

2,6-TDI 94

3,3'-Dichloro-4,4'-diaminodiphenylmethane 94

4-Chlorophenol 28,33

9-Bromoanthracene 14

9-Fluorenylmethyl chloroformate (FMOC-Cl) 9

17β-Estradiol 88

α-Estradiol 88

α-Endosulfan 14

β-Estradiol 88

β-Endosulfan 14

AA 49,50,61,62,63,64,69,113,125,126

ABS 115

Acenaphthene d10 28,33

Acephate 11,12

Acetaldehyde 97,98,99

Acetone 29,96,98,99

Acetonitrile 7,8,9,10,11,23,24,59,60,82,94,96, 98,100

DESCRIPTION PAGE

Acetylacetone 101

Acrolein 97,99

Acrylamide 43,44

Acrylamide Br 43

Acrylonitrile 103,104,115

Acrylonitrile-Butadiene-Styrene (ABS) Resin 115

Actinomycetes 40

Additional Method 9 7






ADI 45

ADU-1 51,91

Al 51,65,67,78,92

Al2O3 119

Alachlor 14

Aldehyde 96,97,98,99,100

Alkyl mercury 83,84,125

Allyl chloride 86

Ammonium citrate 72

Ammonium ion 3

Amosite 118

AMPA (amino methyl phosphoric acid) 9

Anilofos 14

Anionic surfactant 23

Anthracene-d 14

Antigorite 117

Apodize Function 114,127

AQUA Trap 1 87

AQUATIC 35,62,86,105

AQUATIC2 31

AQUATIC-H 87

Argon 62,106

Arsenic 69,113,125

Arsenic hydride 69

As 49,51,67,92,107,108,109,

111,116,125, 126, 130,133

Asahipak NH2P-50 74

Asbestos 117,118

Asulam 7,11,12,59

Atmospheric dust 107,108,109

Atomic absorption spectrometry 62,125,126

ATR 114,115

Atrazine 14

Azoxystrobin 10,11,12,59,60

B 51,65,66,67,76,77,92,125

Ba 67,76

BaO 119

BCR-176 116

DESCRIPTION PAGE

135

INDEX

Be 67,107,108,109,119,126

Bendiocarb 5

Benfluralin 14

Benfuracarb 11

Benomyl 11

Bensulfuron-methyl 10,11,12

Bensulide (SAP) 11,12,59

Bentazon 10,11,13,14

Benzaldehyde 97

Benzene 31,36,84,87,90,103,104,105,124

Bi 67

Bifenox 14

Bisphenol A (BPA) 81,82

Bis-Tris (bis(2-hydroxyethyl)iminotris(hydroxymethyl)methane)

2,54,57,70,93

Blue-green algae 24,79,80,85

Boron 125

Br 20,44,119

Br– 16,20,21,53,54,57,74

BrO3– 16,17

Bromate ion 16

Bromide ion 20,43,74

Bromination 43

Bromobutide 14

Bromochloroacetonitrile 25,26

Bromochloromethane 86

Bromodichloromethane 31,36,86,90,124

Bromoform 31,36,87,90,124

Bromomethane 86,104

Buprofezin 14

Butamifos 14

Butyraldehyde 97,99

C10 23

C11 23

C12 23

C13 23

C14 23

Ca 61,65,67,76,77

Ca2+ 3,4,55,56,58,68,70,71

Cafenstrole 14

Calcium 3,47,51,61

Canister 104,105

CaO 119

Captan 14

Carbaryl 5,11,12

Carbofuran 5,10,11,12

Carbon tetrachloride 31,87,90,104

Carpropamid 11,12

Cd 51,63,65,67,78,92,107,108,

109,111,116,125,126,130,133

Cadmium 63,113,125,126

DESCRIPTION PAGE

Chloral hydrate 25,26,32

Chloramine T 18

Chlorate 21

Chloride ion 20,74

Chlorine 1,21,27,46,47

Chlorine dioxide 21

Chlorite 21

Chlornitrofen 14

Chloroacetic acid 27,33

Chloroacetic acid methyl ester 33

Chloroacetonitrile 25

Chlorobenzene 86,104

Chloroethane 86,104

Chloroethene 103,104,105

Chloroform 31,36,37,87,90,103,104,105,124

Chloromethane 86,104

Chloroneb 14

Chlorothalonil 14

Chlorpyrifos 14

Chromium 63,113,125,126

Chrysotile 117,118

cis-1,2-Dichloroethene 36,104,124

cis-1,2-Dichloroethylene 31,87,90

cis-1,3-Dichloropropene 31,36,87,90,104,124

Cl 20,119

Cl– 1,2,20,21,53,54,57,70,73,74,89,93

Clean Air Act 97

ClO2– 21

ClO3– 21

CN– 19

CNCl 18,19

CNP-amino 14

Co 108

CO2 106,119

CO32– 2,54,57

Copper 51,67,91,108,110,113,116,129,132

Core sampler 127

Cr 51,63,65,66,67,78,92,107,108,

109,111,116,125,126,131,133

Cr6+ 108,116,125

Cr2O3 119

Cu 51,65,67,78,92,111,116,126,131,133

CuO 119

Cyanide ions 18,19

Cyanogen chloride 18,19

Cycropentane 86

CyDTA 45

D2 method 61

Daimuron 10,11,13

DB-1 25,85,99,103,121

DB-5 41,122

DESCRIPTION PAGE

136

INDEXINDEX

DB-5H 88

DB-624 123,124

DB-VRX 90,120

DB-WAX 43

Decadienal 42

Diamond prism 114

Diazinon 14

Dibromoacetonitrile 26

Dibromochloromethane 31,36,86,87,90,124

Dibutyl Tin 122

Dichlobenil 14

Dichloroacetic acid 27,33

Dichloroacetic acid methyl ester 33

Dichloroacetonitrile 26,32

Dichloroisocyanuric acid 46

Dichloromethane 31,36,45,87,88,90,102, 103,104,105,124

Dichlorvos 14

Dimepiperate 14

Dimethametryn 14

Dimethoate 10,14

Dimethyl arsenic 69

Diphenylamine (DPA) 99

Diphenylcarbazide 126

Diphenyl Tin 122

Dipicolinic acid 56

Diquat 6

Disinfection byproduct 16,21,27

Dithiopyr 14

Diuron 10,11,12

DLATGS 114

DNPH (dinitrophenylhydrazine) 97,99,100

Drinking Water Test Method 3,5,22,24,25,35,38,40,41

43,44,45,51,53,57,123

D-TG (differential thermogravimetry) 117

ECD 43,83,90,106,112

Edifenphos 14

EDTA 45

EDTA2Na 82

Electric conductivity detector 4,53,54,55,56,57,58,

68,70,71,73,89,93

Electro-thermal atomization 49,50,63

Endocrine disruptor 81

EPA (American Environmental Protection Agency) 51,91,97,104

Epichlorohydrin 37

EPN 14

Esprocarb 14

Estriol 88

Estron 88

Ethofenprox 59,60

Ethyl acetate 28,43,44,88,100,121

Ethylbenzene 86,104,120

DESCRIPTION PAGE

Ethyl chloride mercury 83

Ethylenediamine 45,68

Ethylenediamine tetraacetic acid (EDTA) 45

Ethyleneimine 94

Ethylthiometon 14

Ethynyl estradiol 88

Etofenprox 14

Etridiazole 14

F 20,53,125

F– 1,2,20,21,53,54,57

FAO and WHO 45

Fe 51,65,66,67,78,92,133

Fe2O3 119

Fenitrothion 14

Fenobucarb 14

Fenthion 14

Flame atomic absorption spectrometry 62,125,126

Flazasulfuron 10,11,12,59,60

Florisil /C18 cartridge 88

Fluorescence detector 5,8,9,23,72,81

Fluorine 1,89

Flutolanil 14

Fly ash 110,111,113,116

FMOC 9

Formaldehyde 32,72,96,97,98,99,101

FPD 121,122

FP method 119

Freon 11 104

Freon 12 104

Freon 113 104

Freon 114 104

FTD 99,100

Fthalide 14

FTIR 114,115,127,128

Furnace method 49,50,63

GC 83,84,90,99,100,106,112,120,121,122

GC/MS 90,102,103,104,105,120,121,122,123,124

Geosmin 38,39,40,41

GL Trap 31,37

GL Trap 1 35,38

Glyphosate 9

Golden algae 42

Golf course pesticide 59,60

Gradient 5,10,11,24,59,96,97,98

Graphite carbon black 102

Groundwater 48,125

Haloacetic acid 27,32,33

Haloacetonitrile 25,26

Halogen compound 44

DESCRIPTION PAGE

137

INDEX

Halosulfuron-methyl 10,11,13,59,60

Happ-Genzel 114,127

HCl 28

Headspace 30,40,41,42,90,120,123,124

Heptadienal 42

Hexachloro-1, 3-butadiene 104

Hexanaldehyde 97

Hexavalent chromium 113,125,126

Hg 92,108,111,116,125,130,133

H2O2 93

Hot spring water 68,69

Hydroxy methansulfonic acid 72

i-Butylaldehyde 99

IC method 3

ICP-AES 65,66,76,77,78,107,125,131,132,133

ICP/MS 51,67,91,92,108,109,110,

111,116,125,129,130,132,133

Iminoctadine Triacetate 8

Industrial waste 112,113,115,116,117,119,126,129

Inert Cap1 38

Insulating oil 112

Interference inhibitor 126

Ion Chromatograph 1,2,3,4,20,21,53,54,55,56,

57,58,68,70,71,72,73,89,93

Ion exchange cartridge 100

Iprobenfos 14

Iprodione 7,11,12,14,59

Isobutane 44,85,88

Isocyanuric acid 22,46

Isofenphos 14

Isoindole derivative 72

Isoprocarb 14

Isoprothiolane 14

Isoxaben 59

Isoxathion 14

i-Valealdehyde 99

JAC 0031 62

JAC 0032 62,65

JEAC 112

JIS K0102 91,116,126,129,132

JIS K0303 101

JSAC0401 126

JSAC0411 125

JWWA 51

K 76,77

K+ 3,4,55,56,58,70,71

Ketonic product 97

K2O 119

Kramers-Kronig 127

DESCRIPTION PAGE

La 61

Lanthanum 61

LC 5,6,7,8,9,10,16,17,18,19,22,23,59,60,

72,74,75,79,80,81,82,94,95,96,97,98

LC/MS 10,11,12,13,24

L-column ODS 10,11

L-cysteine hydrochloride monohydrate 84

Leachate 47

Lead 51,94,96,102,104,113,120,125,126

Li 76

Li+ 55,56

Lithium ion 3

Lizardite 117

Magnesium 3,61,126

Magnesium nitrate 126

Malathion 14

Mapping 127,128

Matrix modifier 49,50

MBC (Methyl 2-bebzimidazolylcarbamate) 11,12

MCT 127

m-Dichlorobenzene 104

Mecoprop 11,13,14,59

Mefenacet 14

MEK 99

Membrane filter 1,2,3,4,53,54,55,56,57,58,68,70,

71,73,74,75,82,89,93,94,95,123,125

Mepronil 14

Mercury 83,84,113,125

Metalaxyl 14

Methacrolein 97

Methidathion 14

Methomyl 5,11,12

Methyl chloride mercury 83

Methyldymron 14

Methyl-t-butyl ether 31,86,120

Mg 61,65,67,76,77

Mg2+ 3,4,55,56,58,61,68,70,71

MgO 119

MIBK 99

Microcystin 79

Microcystin L R 24,79,85

Microcystin R R 24,79

Microcystin Y R 24,79

Mineral water 48

MMPB (2-methyl-3-methoxy-4-phenylbutyric acid) 85

Mn 51,65,67,78,92,107,108,109,111,131,133

MnO 119

Mo 51,65,67,76,77,78,111,130

Molinate 14

Monobutyl Tin 122

Monomethyl arsenic 69

DESCRIPTION PAGE

138

INDEXINDEX

Monophenyl Tin 122

Mortar 117

m,p-Xylene 31,36,37,87,103,104,120,124

MTBE 120

Musty odor 38,40,41

Na 65,67

Na+ 3,4,55,56,58,70,71

NaHCO3 1,16,20,53,125

Na2O 119

NaOH 5,8,75,93

Napropamide 14

n-Butylaldehyde 97

NCI (negative chemical ionization) 44,88

NDG 129

NH4+ 4,55,56,70,71,74,75

n-Hexane 86,103

Ni 51,65,67,78,92,107,108.109,111,116,131,133

NIES 125,131

Ninhydryn Solution 8

NiO 119

NIST 61,107,108,110,111

Nitrate nitrogen 1,89

Nitric acid 11,16,49,50,63,76,78,91,

107,108,110,116,126,129,131,132

Nitrite nitrogen 1,20,89

Nitrous oxide (N2O) 106

N-methycarbamate pesticides 5

NO2– 20,21,53,57,70,74

NO3– 1,2,20,21,53,54,57,70,73,74,89,93

N2O5 119

Nonionic surfactant 52

Non-Suppressor System 2,3,4,54,55,56,57,58,

68,70,71,73,89,93

NOX 70,93

n-Valeraldehyde 99

o-Dichlorobenzene 104

ODS cartridge 79

o-Phthalaldehyde (OPA) 5,72,75

Organic Tin 121,122

Oxalic acid 4,56,58,71

Oxine-Cu 11,12,59

o-Xylene 31,36,37,87,104,120,124

Ozone scrubber 100

P 64,76,77

PAR 52

Passive sampling method 105

Pb 50,51,65,66,67,78,92,107,108,

109,111,116,125,126,130,131,133

PbO 119

DESCRIPTION PAGE

p-Bromofluorobenzene 36,124

PCB 112

Pd 49,50

p-Dichlorobenzene 31,36,87,90,124

Pencycuron 14

Pendimethalin 14

Pentavalent arsenic acid 69

PFB derivatization 88

PFBOA 32

PFB reaction liquid 88

Phenanthrene-d 14

Phenol 28,33

Phenthoate 14

Phosphorus 64

Phthalic acid 73,89

p-Hydroxybenzoic acid 2,54,57,70,93

Piperophos 14

PO43– 20,21,54,64,89

P2O5 119

Polyethylene (PE) 108,110,115,125

Polypropyllene (PP) 115

Polystyrene (PS) 115

Polyurethane foam 94

Pond sediment 125,131

Post-column derivatization 5,9

Potassium bromate 16,43,44

Potassium ion 3

Pretilachlor 14

Probenazole 11,12

Procymid 14

Propiconazole 14

Propionaldehyde 97,98,99

Propoxur 5

Propyzamide 14

PROSPEKT 10,24

PVC pipe 47

Pyributicarb 14

Pyridafenthion 14

Pyriproxyfen 14

Pyroquilone 14

Rainwater 70,71,72,73

Rankine 72

Rb2O 119

Reduction vapor method 113

Rh 108,110,119

River water 11,12,13,49,50,53,54,

55,56,61,62,65,66,67,82

Rtx-1 27,28,37,112

Rtx-5MS 14,32,33,34,42

Rtx-624 30

Rtx-1701 29

DESCRIPTION PAGE

139

INDEX

S 76,77

Sb 51,67,111

Se 51,67,92,111,125,126,130

Seawater 63,74,75,76,77,121,122

Selenium 113,125

Sep-Pak Plus tC18 80

Serpentinite 117

Sewage sludge 132,133

Shim-pack Amino-Na 18

Shim-pack FC-ODS 5,98

Shim-pack IC-A1 72,73,89

Shim-pack IC-A3 2,54,57,70,93

Shim-pack IC-C1 68

Shim-pack IC-C3 4,56,58,71

Shim-pack IC-SA2 1,16,20,53

Shim-pack IC-SA3 21

Shim-pack IC-SC1 3,55

Shim-pack ISC-07/S1504Na 75

Shim-pack SPC-RP3 82

Shim-pack VP-ODS 6,7,8,9,23,24,60,82

Shodex RSpak DE-613 22

Si 76,77

Siduron 7,10,11,12,59

Simazine (CAT) 10,14

Simetryn 14

SiO2 119

SLRS-3 61

Snow water 73

SO3 119

SO32– 72

SO42– 1,2,20,21,53,54,57,70,73,74,89,93

Sodium 3

Sodium acetate trihydrate 84

Sodium carbonate 1,53

Sodium citrate 75

Sodium decylbenzenesulfonate 23

Sodium dodecylbenzenesulfonate 23

Sodium hydrogen carbonate 1,53

Sodium perchlorate 8,23,74

Sodium sulfate 27,28,44,84

Sodium tetradecylbenzenesulfonate 23

Sodium thiosulfate 44

Sodium tridecylbenzenesulfonate 23

Sodium undecylbenzenesulfonate 23

Solgel1 45

Solid-phase extraction 6,7,10,11,24,28,29,30,

31,37,40,41,52,79,80,81,88

SOX 70,93

SPME 41

Sr 76,77

SRM1633 110

SRM1648 107,108

DESCRIPTION PAGE

SRM2711 125

SrO 119

STR ODS-II 59,79,94,96,97

Styrene 103,104

Sulfate ion 1

Sulfurous acid ion 72

Suppressor System 1,20,21,53

Surrogate 88

TA 117

Tap water 1,2,3,4,5,8,10,16,18,20,21,23,24,25,27,

28,29,35,36,38,39,40,41,43,46,48.49,

50,51,52,53,57

Tartaric acid 68

TDI (tolylenediisocyanate) 94,95

Te 110

TEKMAR DOHRMANN 87,105

Tenax-Silica gel 123

Terbucarb (MBPMC) 14

Tetrabutyl Tin 121,122

Tetrachloroethene 36,102,103,104,105,124

Tetrachloroethylene 31,87,90,124

Tetrachloromethane 36,124

Thenylchlor 14

Thermon-HG 83

THF 96,97,98

Thiobencarb 10,14

Thiodicarb 11,12

Thiophanate-methyl 7,11,12

Thiram 10,11,12,59

Threshold value 38,40,41

TiO2 119

Tl 108,116

TMS 32,88

TMS imidazole 88

TMS-phenol 33

TOC 46,47,48

Tolclofos-methyl 14

Toluene 31,36,37,52,87,103,104,120,124

Toluene-d8 104,105

trans-1,2-Dichloroethene 36,124

trans-1,2-Dichloroethylene 31,37,87,90

trans-1,3-Dichloropropene 31,36,87,90,104,124

Tribromide ion method 16

Tributyl Tin 121,122

Trichlorfon 14

Trichloroacetic acid 27,33

Trichloroacetonitrile 26

Trichloroethene 36,102,103,104,105,124

Trichloroethylene 31,87,90

Trichloroisocyanuric acid 46

Triclopyr 10,11,13,14,59

DESCRIPTION PAGE

140

INDEXINDEX

Tricyclazole 11,12

Triethylamine 43,44

Trifluralin 14

Trihalomethane 87

Trimethyl arsenic 69

Triphenyl Tin 121,122

Trivalent arsenous acid 69

U 51,67,111

Uranium 37,51

Underground water 78

Valeraldehyde 97,99

Vinyl chloride 86,119

Vinyl chloride monomer 37

VOC (volatile organic compound) 14,31,35,36,37,86,87,

90,102,103,104,105,123,124

VPC-10 97,101

Wastewater 35,53,57,64,89,90,91,92,116,123,132

Wastewater Standards 35,123

Water bloom 79

Water-quality Control Standards 7,8,9,11,14,32

Waterworks Law 14,29,30,32,33,34,46,47,48,51

XRD 118

XRF 119

Y 65,108,116

Y2O3 119

ZB-WAX 44

Zinc 62,113

Zn 51,62,65,67,78,92,111,116,126,131,133

ZnO 119

DESCRIPTION PAGE DESCRIPTION PAGE

Printed in Japan 3295-02706-10A-IK

The contents of this brochure are subject to change without notice.

JQA-0376

SHIMADZU CORPORATION. International Marketing Division3. Kanda-Nishikicho 1-chome, Chiyoda-ku, Tokyo 101-8448, Japan Phone: 81(3)3219-5641 Fax. 81(3)3219-5710URL http://www.shimadzu.com

Founded in 1875, Shimadzu Corporation, a leader in the development of advanced technologies, has a distinguished history of innovation built on the foundation of contributing to society through science and technology. We maintain a global network of sales, service, technical support and applications centers on six continents, and have established long-term relationships with a host of highly trained distributors located in over 100 countries. For information about Shimadzu, and to contact your local office, please visit our Web site at www.shimadzu.com

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