Japan Kiwao Kadokami Masashi Yanagita a nd Keita Mochinaga The University of Kitakyushu JAPAN June 10 2015 UOK Lab for Envi Pre Anal 1 Todays Contents Background Introduction of Kitakyushu City ID: 804930
Download The PPT/PDF document "Screening analysis of 1170 organic micro..." is the property of its rightful owner. Permission is granted to download and print the materials on this web site for personal, non-commercial use only, and to display it on your personal computer provided you do not modify the materials and that you retain all copyright notices contained in the materials. By downloading content from our website, you accept the terms of this agreement.
Slide1
Screening analysis of 1170 organic micro-pollutants in sewage treatment plants in Kitakyushu, Japan
Kiwao Kadokami, Masashi Yanagita, and Keita MochinagaThe University of Kitakyushu, JAPAN
June 10, 2015
UOK, Lab for Envi Pre Anal
1
Slide2Today’s Contents
BackgroundIntroduction of Kitakyushu CityAutomated Identification and Quantification System (AIQS) for GC-MS and LC-TOF-MSComprehensive analytical methods using two AIQSsObjectivesOutline of resultsMajor chemical groups detectedEmission amounts Change in concentrations during treatment processes
Risk evaluation
Conclusions
June 10, 2015
UOK, Lab for Envi Pre Anal
2
Slide3Population:
957,597 (April 2015)Area: 487.89km
2
(Oct 2010)
GDP:
29.6 billion US$
(
2014)
Slide4Major 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.
UOK, Lab for Envi Pre Anal
4
Slide5Dawn of Industrial Modernization
in Kitakyushu
Yahata Steel Works (Japan’s first state-owned steel works)
began operation
in
1901.
June 10, 2015
UOK, Lab for Envi Pre Anal
5
Slide6Overcoming Severe Pollution:
Kitakyushu’s Experience
1960s
Today
Slide7Selected as OECD
Green Growth
Model City
Other cities selected include Paris, Chicago, Stockholm
L: Ms.
Yoshie
Nakatani
(Director, OECD Tokyo
); R: Mayor of Kitakyushu
Slide8waste
Garbage incinerator
Commute, leisure
Transportation
Standard homes
products
Chemical plants
Processing plants
Mine, oil mine
Fields
Offices
Factories , work shops
use
use
use
use
use
use
waste
cosmetics
pesticides
(paradichlorobenzene)
(LAS)
(
antibacterial agent
)
(glutamic sodium)
(nylon)
(vinyl acetate)
(benzene)
(toluene)
(trichlorethylene)
(tetrachloroethylene)
(organophosphorus
agents)
(fine ceramics
(polyethylene)
(polyvinyl chloride)
(polyester)
(ester)
Raw materials
Intermediates
Chemicals are
Indispensable
M
aterials
for
Modern
S
ociety
June 10, 2015
UOK, Lab for
Envi
Pre Anal
8
Slide9Chemicals Existing in the Aquatic Environment in JapanThe 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.
9Summary of results from 1974 to 2013.WaterSediment
Fish
Air
Diet
Others
Total
Chemicals Surveyed
1095
1026
473
455
27
26
1250
Chemicals Detected
391
470
288
322
21
13
705
Detection Ratio, %
3646
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
Slide10Instruments for Chemical Analysis
VolatileSemi-volatileNon-volatile
Polar
alcohols
ketones
carboxylic acids
alcohols
ketones
carboxylic acids
phenols
high molecular electrolytes carbohydrates
fulvic
acid
Semi-polar
ethers
esters
aldehydes
ethers
esters
aldehydes
epoxidesheterocyclic compoundsproteincarbohydrateshumic acids
Non-polaraliphatic compoundsaromatic compoundsaliphatic compoundsaromatic compoundsalicyclic compounds
non-ionic polymerslignin
Small
MediumLarge10
GC-MS
Derivatization
LC-MS
June 10, 2015
UOK, Lab for Envi Pre Anal
Slide11Automated Identification and Quantification System (AIQS) for GC-MSandComprehensive Analytical Method for SVOCsJune 10, 2015
UOK, Lab for Envi Pre Anal11
Slide12What is AIQS?
Data Registered in AIQS12
Mass spectra
Retention times
(PTRI)
Calibration curves
(
IS)
Results
A
utomated
I
dentification
and
Q
uantification
S
ystem with a
D
ata
BaseJune 10, 2015UOK, Lab for Envi Pre AnalNo use standard substancesReduce time, cost and waste Simultaneous measurement
Slide1313GC-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 June 10, 2015UOK, Lab for Envi Pre Anal
Slide14Measurement Procedures by AIQSJune 10, 2015UOK, Lab for Envi Pre Anal
14Measure sample
Calculate RT
Compare RT and mass to standard
Calcurate
amount
Exist?
Last
Start
END
YES
YES
NO
NO
Next
Analytical data
Available as commercial product
Pretreatment
Measure CS
Database (RT, Mass and Cal)
No use standard substances
Reduce time, cost and waste
Simultaneous measurement
Slide15Substances Registered in the AIQS
Class 1NumberClass 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
15
June 10, 2015
January 1, 2014
UOK, Lab for Envi Pre Anal
Slide16Performance of AIQS for GC-MSJune 10, 2015UOK, Lab for Envi Pre Anal
16ItemPerformancePrediction of retention times (RT)Difference between actual and Predicted RT is less than 3 s.Measurement reproducibilityReproducibility (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.
Slide17Flowchart of SVOCs Analysis
17June 10, 2015UOK, Lab for Envi Pre Anal
Slide18Development of Analytical Methods for Water Samples using Model CompoundsJune 10, 2015
n-AlkanesAliphatic acid estersAlcohols
Phthalates
Ethers
Phosphate esters
Benzenes
Organochlorine pesticides
Biphenyls
Organophosphorus pesticides
Nitrobenzenes
Carbamate pesticides
Polycyclic aromatic
hydrocarbons (PAH)
Carbamide pesticides
Nitro-PAHs
Acid aminde pesticide
Heterocyclics
Triazine pesticide
Phenols
Dinitroaniline pesticide
Nitrophenols
Diphenylether pesticide
Amines
Pyrethroid type pesticide
Aromatic amines
Other pesticides
Sulfonate
57 groups, 202 compounds
b
p
: 145
~
536
℃
,
logPow
: -0.65
~
15.07
18
UOK, Lab for Envi Pre Anal
Slide19Recoveries by LLE with CH2Cl2June 10, 2015
19UOK, Lab for Envi Pre AnalBar shows 95% confidence interval of average. J. Environ. Chem, 19, pp351-360, 2009.Anal. Sci., 29, pp483-486, 2013.
Slide20Method Detection Limit of Water, ng/l
Compounds GC-MS TIMGC-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
-
-
20
June 10, 2015UOK, Lab for Envi Pre Anal
Slide21AIQS and Comprehensive Method for Polar Chemicals using LC/TOF-MS21June 10, 2015
UOK, Lab for Envi Pre Anal
Slide22LC-TOF-MS Conditions
LCAgilent 1200ColumnGL Science ODS-4 HP (150mm, 2.1mm, 3µm)Column temp.40℃Flow rate
0.3mL/min
Mobile phase
A: 5mM CH
3
COONH
4
in H
2
O
B: 5mM CH
3
COONH
4
in CH
3
OH
Gradient profile
Time[min]03050B[%]59595
MSAgilent 6220 Time of Flight LC/MSIonizationESI-positiveMeasurement modeScan Scan range
50-1000Reference ion m/z=121.050873,922.009798Drying gas 10L/min at 325℃Nebulizer gas pressure50psiVcap voltage
3500V Fragmentor voltage
100V (100, 150, 200 and 250V)
22June 10, 2015UOK, Lab for Envi Pre Anal
Slide23PPCPs: Pharmaceutical and Personal Care Products
ClassNumberExampleIndustrial chemicals6Flame retardant, etc.PPCPs95Antibiotic, Analgesic, etc.Pesticides207Fungicide, Herbicide,
etc.Total
308
Substances Registered in AIQS
for LC-TOF-MS
23
June 10, 2015
UOK, Lab for Envi Pre Anal
Slide24Identification PerformanceCorrect identification can be done using both RT and exact mass (mass resolution = 10000).In addition, target screening of a large number of substances is possible by using in-source fragment ions.
June 10, 2015UOK, Lab for Envi Pre Anal24TICCISTargetFragment ions
Target
Slide25Flowchart of Polar Substances Analysis
25June 10, 2015UOK, Lab for Envi Pre AnalChemosphere, 122, pp125-130, 2015.
Slide26Recoveries by SPE with PS-2+AC-2June 10, 2015
26UOK, Lab for Envi Pre AnalBar shows 95% confidence interval of average.Conc: 0.2 mg/L, n=7
Slide27Spike amounts,
μgnAvg recovery, %AvgRSD, %
No of comp recovered > 70%
High Conc.
(0.5ppb)
100
8
81
(87)
※
13
102/126
Low Conc.
(0.1ppb)
20
8
75
(80)
※
2594/12614
※ Excluding comp over log Pow 4.5
Recovery Test
Slide28Method Detection Limit of Water, ng/l
MDL, ng/LNo of comp2.5
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
Slide29Objectives
To clarify the types and quantities of organic micro-pollutants (OMPs) discharged from domestic activitiesTo clarify emission amounts per capitaTo clarify treatment efficiency of STPs by the activated sludge methodTo clarify the types and quantities of OMPs discharged to the environment June 10, 2015UOK, Lab for Envi Pre Anal29
Slide30Study Sewage Treatment Plants
https://www.city.kitakyushu.lg.jp/files/000096297.pdf30
Kitaminato STP
Treatment population
:
91,796
Treatment capacity
:
44,000m3/d
Hiagari
STP
Treatment population
:
34,7367
Treatment capacity
:
263,000m3/d
Shinmachi
STP
Treatment population
:102,151
Treatment capacity: 64,000m3/dKogasaki STPTreatment population:298,298Treatment capacity
:177,000m3/d
Sone
STPTreatment population:140,108Treatment capacity: 73,000m3/d
Sampling date: Oct 29, 2014
A sewerage coverage ratio in Kitakyushu is 99.8%.
Activated sludge treatment method
Slide31https://www.city.kitakyushu.lg.jp/suidou/04600128.htmlSampling Points
Grit camberPrimary sedimentation tankFinal sedimentation tank
Activated sludge tank
Chlorine disinfection
Influent
Primary treatment water
Effluent
Sludge treatment facility
Sea
Drain
June 10, 2015
UOK, Lab for Envi Pre Anal
31
Slide32ResultsJune 10, 2015UOK, Lab for Envi Pre Anal32
Slide33Recovery of Surrogates, %33
GC-MS method, n=15Error bar is 95% CL.
Slide34June 10, 2015
UOK, Lab for Envi Pre Anal34
Recovery of Surrogates, %
L
C-TOF-MS method, n=15
Recovery, %
Error bar is 95% CL.
Slide35The number of detected substances and their concentrations at each STPJune 10, 2015UOK, Lab for Envi Pre Anal
35A-GC: After grid chamberA-PST:After primary sedimentation tankA-FST:After final sedimentation tank
Slide36Concentrations (mg/L) of the chemicals found and the numbers of chemicals found
Target substanceInfluent(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)88.4Pesticides (574)0.11 (5)
0.11 (6)
0
Total (1170)
665 (124)
16.9
(90)
97.5
June 10, 2015
UOK, Lab for Envi Pre Anal
36
(Number of substances)
Slide37The number of detected substances and their concentrations at each STP
NamePointNumber of detected compoundsTotal concentration, m
g/L
Sone
A-GC
115
786.7
A-PST
113
658.3
A-FST
68
15.9
Shinmachi
A-GC
106
755.9
A-PST
107
613.9
A-FST
67
19.7
Hiagari
A-GC111
585.3
A-PST
109
488.3
A-FST
72
17.9
Kitaminato
A-GC
108
648.8
A-PST
108
634.6
A-FST
64
19.8
Kogasaki
A-GC
101
550.0
A-PST
98
451.4
A-FST
57
11.1
June 10, 2015
UOK, Lab for Envi Pre Anal
37
A-GC:
After grid chamber
A-PST:
After primary sedimentation tank
A-FST:
After final sedimentation tank
Slide38Substances detected at the 10 highest concentration in influents or effluents
NoInfluentEffluentCompoundConc, ug/LCompoundConc, ug/L
1
Cholesterol
136.6
Metformin
2.87
2
Coprostanol
64.1
Bis
(2-ethylhexyl)phthalate
1.96
3
2-Phenoxy-e
thanol
35.9
Cholesterol
1.95
4beta-Sitosterol35.4Crotamiton1.8453-&4-Methylphenol33.7
Azithromycin 1.056Epicoprostanol29.7Sulpiride0.987Campesterol
27.2Etodolac
0.6782-Butoxyethanol
23.2Coprostanol0.659L-Menthol21.0Diethyl phthalate0.6310Caffeine
20.1
Clarithromycin
0.59
June 10, 2015
UOK, Lab for Envi Pre Anal
38
Slide39Drugs detected at the 10 highest concentration in influents or effluentsCompound
Conc. ug/LAmountkg/dClassAcetaminophen12.605.86 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
B
ronchodilatorBezafibrate2.661.36 Lipid regulatorsCrotamiton2.240.94
Anti-itch medicationIbuprofen1.790.55 Analgesics/anti-inflammatoricsKetoprofen1.610.67
Analgesics/anti-inflammatoricsClarithromycin
0.860.39
AntibioticsJune 10, 2015UOK, Lab for Envi Pre Anal39CompoundConc. ug/LAmountkg/dClass
Metformin
2.87
1.10
Antidiabetics
Crotamiton
1.84
0.79
Anti-itch medication
Azithromycin
1.05
0.45
Antibiotics
Sulpiride
0.98
0.42
Antidepressant
Etodolac
0.67
0.27
Analgesics/anti-
inflammatorics
Clarithromycin
0.59
0.26
Antibiotics
Lidocaine
0.49
0.21
Local anesthetic
Sulfamethoxazole
0.31
0.17
Antibiotics
Atenolol
0.37
0.15
Beta-blockersBezafibrate0.300.14Lipid regulatorsInfluentEffluent
Concentration is the average of the 5 STPs.
Amount is the sum of the 5 STPs.
Slide40Quantities of the detected substances at each sampling point
NamePointAll substances, kg/dayPPCPs, kg/dayWater volume, ton/day
Sone
A-GC
37.7
5.32
47,964
A-PST
31.6
4.38
A-FST
0.76
0.52
Shinmachi
A-GC
34.3
4.75
45,413
A-PST
27.9
4.53
A-FST
0.90
0.48
Hiagari
A-GC
106.2
18.2
181,388
A-PST
88.6
16.6
A-FST
3.25
1.83
Kitaminato
A-GC
25.8
3.29
39,706
A-PST
25.2
3.61
A-FST
0.79
0.57
Kogasaki
A-GC
75.5
10.5
137,217
A-PST
61.9
10.4
A-FST
1.52
1.10
Whole city
A-GC
279.5
42.1
451,688
A-PST
235.2
39.5A-FST7.224.50June 10, 2015UOK, Lab for Envi Pre Anal40A-GC:
After grid chamberA-PST:After primary sedimentation tankA-FST:After final sedimentation tank
Slide41Per capita daily discharged quantities of the detected substances
Amounts, mg/capita/dayAll substancesPPCPsInfluent29244Effluent7.54.7June 10, 2015UOK, Lab for Envi Pre Anal41
Slide42Low removal substances and substances whose concentrations in effluent are higher than in influentSubstance
STP1,2,3-Trimethoxybenzene5/52,6-Di-tert-butyl-4-benzoquinone5/5
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
4/5Anthraquinone3/5n-C25H522/5n-C26H54
2/5
2(3H)-Benzothiazolone2/5
2-(Methylthio)-benzothiazol2/5Tris(2-chloroethyl) phosphate2/5Dicyclohexylamine2/5
Sulfapyridine
2/5
June 10, 2015
UOK, Lab for Envi Pre Anal
42
Effluent
conc
> Influent
conc
Slide43Compounds detected over PNEC
(Ratio of MEC to PNEC)June 10, 2015UOK, Lab for Envi Pre Anal43Compound
Sulfamethoxazole
Clarithromycin
Azithromycin
Max
19.9
11.8
9.3
Min
6.1
6.4
4.8
Average
11.6
8.4
7.0
PNEC*,
m
g/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.
June 10, 2015
UOK, Lab for Envi Pre Anal
44
Slide45Thanks for your attention!!