Kiwao Kadokami, Masashi Yanagita, and Keita Mochinaga The University of Kitakyushu, JAPAN June 10,...

Screening analysis of 1170 organic micro-pollutants in sewage treatment plants in Kitakyushu, Japan

Kiwao Kadokami, Masashi Yanagita, and Keita Mochinaga

The University of Kitakyushu, JAPAN

June 10, 2015 UOK, Lab for Envi Pre Anal 1

UOK, Lab for Envi Pre Anal 2

Today’s Contents Background

Introduction of Kitakyushu City Automated Identification and Quantification

System (AIQS) for GC-MS and LC-TOF-MS Comprehensive analytical methods using two

AIQSs Objectives Outline of results Major chemical groups detected Emission amounts Change in concentrations during

treatment processes Risk evaluation Conclusions

June 10, 2015

Population: 957,597 (April 2015)Area: 487.89km2 (Oct 2010)GDP: 29.6 billion US$ (2014)


Major enterprises in the City

Mitsubishi Chemical Corporation

Nippon Steel & Sumitomo Metal

TOTO LTD

Kyushu Electric Power Co.,Inc.

Toyota Motor Corporation Nissan Motor Co., Ltd.


Dawn of Industrial Modernization in Kitakyushu

Yahata Steel Works (Japan’s first state-owned steel works) began operation in 1901.June 10, 2015

Overcoming Severe Pollution:

Kitakyushu’s Experience1960s Today

9

Chemicals Existing in the Aquatic Environment in Japan

The Nation-wide survey by Ministry of the Environment, Japan shows that a large number of chemicals pollute the environment.

More than thousands chemicals including unintentionally created chemicals seem to exist in the aquatic environment.

Summary of results from 1974 to 2013.

Water Sediment Fish Air Diet Other

s Total

Chemicals

Surveyed1095 1026 473 455 27 26

1250

Chemicals

Detected391 470 288 322 21 13 705

Detection Ratio, % 36 46 61 71 78 50 56

Highly efficient analytical methods are necessary.

In order to examine pollution by chemicals, we have to measure as many substances as possible.

June 10, 2015 UOK, Lab for Envi Pre Anal


Automated Identification and

Quantification System (AIQS) for GC-MS

andComprehensive

Analytical Method for SVOCs

June 10, 2015

100 200 300 4000.0

25.0

50.0

75.0

100.0

%

198

255 442441277751

110 275206

443296167 365

What is AIQS?Data Registered in AIQS

12

100 200 300 4000.0

25.0

50.0

75.0

100.0

%

198

255 442441277751

110 275206

443296167 365

0.0 5.0 ”Z“x”ä0.000

0.025

0.050

0.075

0.100

0.125

0.150

0.175–ÊÏ”ä(x100)

Mass spectra

Retention times(PTRI)

Calibration curves

(IS)

ResultsResults

Automated Identification and

Quantification System with a

DataBase


No use standard substancesReduce time, cost and waste Simultaneous measurement

13

GC-MS 　： GC-Quadrupole MS 　[GC] 　　　　　　　

Column 　： J&W DB-5 MS (30 m×0.25 mm i.d, 0.25

µm film)Column oven temp.

： 40 ℃(2 min) - 8 ℃/min - 310 ℃(5 min)

　

Injection temp. ： 250 ℃

　　　　　

Injection mode： Splitless, 1 min for purge-off time 　

　

Carrier gas ： He 　　　　　

Linear velocity ： 40 cm/s, constant flow mode

　　

[MS] 　　　　　　　

Interface temp. ： 300 ℃

　　　　　

Ion source temp.

： 200 ℃

　　　　　

Ionization method ： EI 　　　　　

Tuning method ： Target tuning for US EPA method 625

　

Measurement method

： SIM/Scan (m/z 45 to 600) 　

　　

GC-MS Conditions 　


Substances Registered in the AIQS　

Class 1 Number Class 2 Number

Chemicals consisting of C and H 195

PAHs 79

PCBs 62

Others 54

Chemicals consisting of C, H and O 150

Phenols 50

Others 100

Chemicals containing N

113

Aromatic amines 43

Nitro compounds 42

Others 28

Chemicals containing S 12 12

Chemicals containing P 8 8

PPCPs 14 14

Pesticides 451

Insecticide 184

Herbicide 118

Fungicide 116

Others 33

Total 943 15June 10, 2015 January 1, 2014UOK, Lab for Envi Pre Anal

Performance of AIQS for GC-MS


Item PerformancePrediction of retention times (RT)

Difference between actual and Predicted RT is less than 3 s.

Measurement reproducibility

Reproducibility (RSD) of 78% of the registered compounds is below 20%.

Instrumental detection limit (IDL)

IDL of 86% of the registered compounds is below 10 pg (scan mode).

J. Chromatogr A, 1089 pp219-226, 2005.Bunseki, 60, pp543-556. 2011.


Flowchart of SVOCs Analysis

GC/MSSIM/Scan

ConcentrationRE, N2 stream, 1 mL, IS

DehydrationNa2SO4

Liquid-liquid ExtractionDichloromethane, twice

Sample1000 mL, pH 7.0, NaCl, Surrogates

June 10, 2015

Recoveries by LLE with CH2Cl2

June 10, 2015 19UOK, Lab for Envi Pre Anal

Bar shows 95% confidence interval of average. J. Environ. Chem, 19, pp351-360, 2009.Anal. Sci., 29, pp483-486, 2013.

Method Detection Limit of Water, ng/l

Compounds

GC-MS TIM

GC-MS SIM

GC-MS-MS

PAHs 10 1 -

Sterols 32-320 8-320 -

PCBs 1.6-40 0.4-1.6 0.4-1.6

Pesticides 20 2 0.1-16

Others 5-500 - -

20June 10, 2015 UOK, Lab for Envi Pre Anal


AIQS and Comprehensive

Method for Polar Chemicals using

LC/TOF-MS

June 10, 2015

LC-TOF-MS ConditionsLC Agilent 1200

ColumnGL Science ODS-4 HP (150mm, 2.1mm,

3µm)Column temp. 40℃

Flow rate 0.3mL/min

Mobile phase A: 5mM CH3COONH4 in H2O

B: 5mM CH3COONH4 in CH3OH

Gradient profileTime[min] 0 30 50

B[%] 5 95 95MS Agilent 6220 Time of Flight LC/MS

Ionization ESI-positiveMeasurement

mode Scan

Scan range 50-1000Reference ion m/z=121.050873,922.009798

Drying gas 10L/min at 325℃Nebulizer gas

pressure 50psi

Vcap voltage 3500V Fragmentor

voltage 100V (100, 150, 200 and 250V)

22June 10, 2015 UOK, Lab for Envi Pre Anal


PPCPs: Pharmaceutical and Personal Care Products

Class Number Example

Industrial chemicals 6 Flame retardant,

etc.

PPCPs 95 Antibiotic, Analgesic, etc.

Pesticides 207 Fungicide, Herbicide, etc.

Total 308

　Substances Registered in AIQS

for LC-TOF-MS

June 10, 2015


Flowchart of Polar Substances Analysis

LC-TOF-MSTIM

ConcentrationN2 stream, 1 mL, IS

ElutionMeOH 5 ml, DCM 5 mL, each

DryN2 stream, 40 min

SPEWaters PS2 and AC2

FiltrationWhatman GF/C

Sample200 mL, pH 7.0, Surrogates

June 10, 2015Chemosphere, 122, pp125-130, 2015.

Recoveries by SPE with PS-2+AC-2

June 10, 2015 26UOK, Lab for Envi Pre Anal

Bar shows 95% confidence interval of average.Conc: 0.2 mg/L, n=7

Method Detection Limit of Water, ng/l

MDL, ng/L No of comp

2.5 55 (44％ )

5.0 32 (25％ )

10 23 (18％ )

20 7 (6％ )

50 6 (5％ )

100 3 (2％ )

The method can determine targets

at ppt level in water.15

Objectives• To clarify the types and quantities

of organic micro-pollutants (OMPs) discharged from domestic activities

• To clarify emission amounts per capita

• To clarify treatment efficiency of STPs by the activated sludge method

• To clarify the types and quantities of OMPs discharged to the environment


Study Sewage Treatment Plants

https://www.city.kitakyushu.lg.jp/files/000096297.pdf

30

Kitaminato STP

Treatment population ： 91,796Treatment capacity ： 44,000m3/d

Hiagari STP


Shinmachi STP

Treatment population ： 102,151Treatment capacity: 64,000m3/d

Kogasaki STP

Treatment population ： 298,298Treatment capacity ：177,000m3/d

Sone STP


Sampling date: Oct 29, 2014

A sewerage coverage ratio in Kitakyushu is 99.8%.

Activated sludge treatment method

https://www.city.kitakyushu.lg.jp/suidou/04600128.html

Sampling Points

Grit camber

Primary sedimentation

tank

Final sedimentation

tank

Activated sludge tank

Chlorine disinfection

InfluentPrimary

treatment water

Effluent

Sludge treatment facility

SeaDrain



Results

June 10, 2015

The number of detected substances and their

concentrations at each STP


A-GC A-PST A-FST A-GC A-PST A-FST A-GC A-PST A-FST A-GC A-PST A-FST A-GC A-PST A-FSTSone Shinmachi Hiagari Kitaminato Kogasaki

0

20

40

60

80

100

120

140

Pesticides

PPPCPs

CHP

CHS

CHN

CHO

CH

Num

ber

of

dete

cted

subst

ance

s

A-GC A-PST A-FST A-GC A-PST A-FST A-GC A-PST A-FST A-GC A-PST A-FST A-GC A-PST A-FSTSone Shinmachi Hiagari Kitaminato Kogasaki

0

100

200

300

400

500

600

700

800

900

Pesticides

PPCPs

CHP

CHS

CHN

CHO

CH

Conce

ntr

ati

on, ug/L

A-GC: After grid chamberA-PST:After primary sedimentation tankA-FST:After final sedimentation tank


Concentrations (mg/L) of the chemicals found and the numbers of chemicals

found Target substance

Influent(after grid chamber)

Effluent(after final

sedimentation tank)

Removal ratio, %

Chemicals consisting of C and H (190) 36 (44) 0.39 (28) 98.9

Chemicals consisting of C, H, and O (159) 532 (37) 4.3 (22) 99.2

Chemicals containing N (118) 1.8 (3) 0.54 (4) 70

Chemicals containing S (12) 0.29 (2) 0.48 (3) -65.5

Chemicals containing P (9) 0.47 (3) 0.27 (3) 42.6

Pharmaceuticals and personal care products (108) 95 (30) 11 (24) 88.4

Pesticides (574) 0.11 (5) 0.11 (6) 0

Total (1170)665

(124)16.9 (90) 97.5

June 10, 2015 (Number of substances)


Substances detected at the 10 highest concentration in influents

or effluentsNo

Influent Effluent

Compound Conc, ug/L Compound Conc,

ug/L

1 Cholesterol 136.6 Metformin 2.87

2 Coprostanol 64.1 Bis(2-ethylhexyl)phthalate 1.96

3 2-Phenoxy-ethanol 35.9 Cholesterol 1.95

4 beta-Sitosterol 35.4 Crotamiton 1.84

5 3-&4-Methylphenol 33.7 Azithromycin 1.05

6 Epicoprostanol 29.7 Sulpiride 0.98

7 Campesterol 27.2 Etodolac 0.67

8 2-Butoxyethanol 23.2 Coprostanol 0.65

9 L-Menthol 21.0 Diethyl phthalate 0.63

10 Caffeine 20.1 Clarithromycin 0.59June 10, 2015


Drugs detected at the 10 highest concentration in influents or

effluents

Compound Conc. ug/LAmount

kg/dClass

Acetaminophen

12.60 5.86 Analgesics/anti-inflammatorics

Metformin 12.16 5.98 Antidiabetics

Etodolac 6.01 2.81 Analgesics/anti-inflammatorics

Azithromycin 3.36 1.46 Antibiotics　

Theophylline 2.85 1.37 Bronchodilator

Bezafibrate 2.66 1.36 Lipid regulators

Crotamiton 2.24 0.94 Anti-itch medication

Ibuprofen 1.79 0.55 Analgesics/anti-inflammatorics

Ketoprofen 1.61 0.67 Analgesics/anti-inflammatorics

Clarithromycin 0.86 0.39 Antibiotics

June 10, 2015

Compound Conc. ug/LAmount

kg/dClass

Metformin 2.87 1.10 Antidiabetics

Crotamiton 1.84 0.79Anti-itch medication

Azithromycin 1.05 0.45 Antibiotics

Sulpiride 0.98 0.42 Antidepressant

Etodolac 0.67 0.27Analgesics/anti-inflammatorics

Clarithromycin 0.59 0.26 Antibiotics

Lidocaine 0.49 0.21Local

anesthetic　Sulfamethoxazol

e 0.31 0.17 Antibiotics

Atenolol 0.37 0.15 Beta-blockers

Bezafibrate 0.30 0.14 Lipid regulators

Influent Effluent

Concentration is the average of the 5 STPs.Amount is the sum of the 5 STPs.


Quantities of the detected substances

at each sampling pointName Point All substances,

kg/dayPPCPs, kg/day

Water volume, ton/day

SoneA-GC 37.7 5.32

47,964A-PST 31.6 4.38A-FST 0.76 0.52

ShinmachiA-GC 34.3 4.75

45,413A-PST 27.9 4.53A-FST 0.90 0.48

HiagariA-GC 106.2 18.2

181,388A-PST 88.6 16.6A-FST 3.25 1.83

KitaminatoA-GC 25.8 3.29

39,706A-PST 25.2 3.61A-FST 0.79 0.57

KogasakiA-GC 75.5 10.5

137,217A-PST 61.9 10.4A-FST 1.52 1.10

Whole cityA-GC 279.5 42.1

451,688A-PST 235.2 39.5A-FST 7.22 4.50

June 10, 2015

A-GC: After grid chamber

A-PST:After primary sedimentation tank

A-FST:After final sedimentation tank


Per capita daily discharged quantities of the detected substances

Amounts, mg/capita/dayAll

substances

PPCPs

Influent 292 44

Effluent 7.5 4.7June 10, 2015


Low removal substances and substances whose concentrations

in effluent are higher than in influent

Substance STP

1,2,3-Trimethoxybenzene 5/5

2,6-Di-tert-butyl-4-benzoquinone

5/5

2-Methylaniline 5/5

Sulfamethoxazole 5/5

Sulpiride 5/5

Candesartan 5/5

Carbamazepin 5/5

1,3-Dicyclohexylurea 4/5

Roxithromycin 4/5

Carbendazim 4/5

Diuron 4/5

Anthraquinone 3/5

n-C25H52 2/5

n-C26H54 2/5

2(3H)-Benzothiazolone 2/5

2-(Methylthio)-benzothiazol 2/5

Tris(2-chloroethyl) phosphate 2/5

Dicyclohexylamine 2/5

Sulfapyridine 2/5June 10, 2015

Chlor

phen

iram

ine

mal

eate

Sulfa

pyrid

ine

Tris(

2-ch

loro

ethy

l) ph

osph

ate

Crota

mito

n

Lidoc

aine

Trim

etho

prim

Dicycloh

exyl

amin

e

Disopy

ram

ide

Clarit

hrom

ycin

Ateno

lol

Tris(

1,3-

dich

loro

-2-p

ropy

l) ph

osph

ate

Losa

rtan

0

5

10

15

20

25

30

35

40

45

Re

mo

va

l ra

te,

%

Effluent conc > Influent conc


Compounds detected over PNEC

(Ratio of MEC to PNEC)

June 10, 2015

CompoundSulfamethoxazo

le Clarithromycin Azithromycin

Max 19.9 11.8 9.3

Min 6.1 6.4 4.8

Average 11.6 8.4 7.0

PNEC*, mg/L

0.027 0.07 0.15* Sci Total Environ, 429, pp123-155, 2012.

Conclusions• 133 out of 1170 analytes with 665 mg/L were

detected in influents. Detected substances were comprised of sterols, PPCPs, phenols, phthalates and PAHs.

• Emission quantities of all analytes and PPCPs are 292 and 44 mg/capita/day, respectively.

• Activated sludge method can remove over 97% of the detected substances except for PPCPs and organophosphorus flame retardants.

• 7.22 kg of analytes and 4.50 kg of PPCPs were discharged from the STPs to the aquatic environment. Several PPCPs have a potential to give adverse effects on aquatic organisms.


Thanks for your attention!!

Kiwao Kadokami, Masashi Yanagita, and Keita Mochinaga The University of Kitakyushu, JAPAN June 10,...

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