Figure S-1. Tokyo Bay basin and sampling sites for river water.

1

Table S-1. List of chemical standards for confirmation and quantificationID Chemical Name Chemical

Formula

CAS Supplier

1 Dihydrochalcone C15H14O 1083-30-3 Wako

2 Iodonaphthalene C10H7I 90-14-2 TCI

3 Benzothiazole, 2-(methylthio)- C8H7NS2 615-22-5 TCI

4 2-(2-Hydroxy-5-methylphenyl)benzotriazole C13H11N3O 2440-22-4 TCI

5 Tetramethyl decynediol C14H26O2 126-86-3 TCI

6 2,6-Di-tert-butyl-1,4-benzoquinone C14H20O2 719-22-2 TCI

7 2-Ethylhexyl trans-4-methoxycinnamate C18H26O3 83834-59-7 Sigma-Aldrich

8 Bumetrizole C17H18ClN3O 3896-11-5 Wako

9 Oxybenzone C14H12O3 131-57-7 TCI

10 Propanoic acid, 3,3'-thiobis-, didodecyl ester C30H58O4S 123-28-4 Wako

11 1(2H)-Naphthalenone, 3,4-dihydro- C10H10O 529-34-0 Wako

12 Hedione C13H22O3 24851-98-7 TCI

13 2-Ethylhexyl 4-Methoxycinnamate C18H26O3 5466-77-3 TCI

14 Cholestanol C27H48O 80-97-7 Alfa Aesar

15 13-Docosenamide, (Z)- C22H43NO 112-84-5 Sigma-Aldrich

16 di-p-Tolyl sulfone C14H14O2S 599-66-6 Alfa Aesar

17 Diethylhexyl adipate C22H42O4 103-23-1 Wako

18 Cyclotrisiloxane, hexamethyl- C6H18O3Si3 541-05-9 Sigma-Aldrich

19 Mirtazapine C17H19N3 61337-67-5 LKT

20 1,3-Dicyclohexylurea C13H24N2O 2387-23-7 Wako

21 N-Butylbenzenesulfonamide C10H15NO2S 3622-84-2 TCI

22 Patchouli alcohol C15H26O 5986-55-0 Carbosynth

23 Pretilachlor C17H26ClNO2 51218-49-6 TCI

24 Phenanthrene, 1-methyl-7-(1-methylethyl)- C18H18 483-65-8 ChromaDex

25 Squalene C30H50 7683-64-9 Echelon

26 Stigmasterol C29H48O 83-48-7 MP Bio

27 TCIPP C9H18Cl3O4P 13674-84-5 Sigma-Aldrich

28 Tributyl acetylcitrate C20H34O8 77-90-7 TCI

29 Hexylcinnamaldehyde C15H20O 101-86-0 Wako

30 Eudesmol C15H26O 473-15-4 Wako

31 β-Sitosterol C29H50O 83-46-5 MP Bio　

32 β-Ionone C13H20O 14901-07-6 Wako

2

ID Chemical Name Chemical

Formula

CAS Supplier

33 Ametryn C9H17N5S 834-12-8 Wako

34 Benzyl Benzoate C14H12O2 120-51-4 Wako

35 Azulol C15H18 489-84-9 TCI

36 Crotamiton C13H17NO 483-63-6 LKT

37 Cholesterol C27H46O 57-88-5 Wako

38 Diphenylamine C12H11N 122-39-4 Wako

39 Diphenyl sulfone C12H10O2S 127-63-9 TCI

40 Dimethametryn C11H21N5S 22936-75-0 Wako

41 Stigmastanol C29H52O 19466-47-8 TCI

42 Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate C30H56N2O4 41556-26-7 TCI

43 Tebuconazole C16H22ClN3O 107534-96-

3

Wako

44 Palmitic acid C16H32O2 57-10-3 Wako

45 Bromopropylate C17H16Br2O3 18181-80-1 Wako

46 Butachlor C17H26ClNO2 23184-66-9 Wako

47 Dicyclohexyl phthalate C20H26O4 84-61-7 Wako

48 Bis(2-ethylhexyl) fumarate C20H36O4 141-02-6 TCI

49 Prometryn C10H19N5S 7287-19-6 Wako

50 Bromobutide C15H22BrNO 74712-19-9 Wako

51 Benzalacetone C10H10O 122-57-6 Wako

52 Malathion C10H19O6PS2 121-75-5 Sigma-Aldrich

53 Isopropyl Myristate C17H34O2 110-27-0 TCI

54 Mefenacet C16H14N2O2S 73250-68-7 Wako

55 TDCPP C9H15Cl6O4P 13674-87-8 Wako

56 TCEP C6H12Cl3O4P 115-96-8 TCI

57 TBEP C18H39O7P 78-51-3 Wako

58 TPhP C18H15O4P 115-86-6 TCI

59 Lup-20(29)-en-3-one C30H48O 1617-70-5 ChromaDex

60 Loratadine C22H23ClN2O2 79794-75-5 TCI

61 1,2,3,6,7,8-Hexahydropyrene C16H16 1732-13-4 Sigma-Aldrich

62 Anthraquinone C14H8O2 84-65-1 Sigma-Aldrich

63 Simazine C7H12C ｌ N5 122-34-9 Wako

64 Trichlorfon C4H8Cl3O4P 52-68-6 Wako

3

ID Chemical Name Chemical

Formula

CAS Supplier

65 Methidathion C6H11N204PS3 950-37-8 Wako

66 n-Eicosane C20H42 052-07721 Wako

67 n-Octadcane C18H38 593-45-3 TCI

68 Cholest-4-en-3-one C27H44O 601-57-0 Sigma-Aldrich

69 Fudiolan C12H18O4S2 50512-35-1 Wako

70 Diazinone C12H21N2O3PS 333-41-5 Wako

71 Cholesta-4,6-dien-3-ol, (3a)- C27H44O 14214-69-8 USP

72 a-Ionone C13H20O 127-41-3 TCI

73 Hexadecanoic acid, methyl ester C17H34O2 112-39-0 Wako

74 Methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate C18H28O3 6386-38-5 Combi-Bio

75 Hexaconazole C14H17Cl2N3O 79983-71-4 Wako

76 t-Butylhydroquinone C10H14O2 1948-33-0 Wako

77 Phytol C20H40O 150-86-7 Wako

78 Ipconazole C18H24ClN3O 125225-28-

7

Wako

79 Dihydroactinidiolide C11H16O2 17092-92-1 Combi-Bio

80 Dimethenamid C12H18ClNO2S 87674-68-8 Wako

81 Musk ketone C14H18N2O5 81-14-1 Sigma-Aldrich

4

Figure S-2. Confidence levels in a compound assignment for GC–(EI)–MS spectra applied in this study.See ref. 1 for the level system in LC–MS.

5

Table S-2 Recovery rate, R2, and LOQ of the quantified 27 compounds

No.

Chemical Name Group Name CASRecovery

(%)(n = 4)

R2LOQ

(ng/L)

1 Tetramethyl decynediol Surfactant 126-86-3 62.2>0.9

91.1

2 Iodonaphthalene PAH 90-14-2 62.4>0.9

90.02

3 Hedione PPCP24851-98-

767.6

>0.99

0.9

4 Azulol PPCP 489-84-9 54.5>0.9

90.08

5 Diphenylamine Pesticide 122-39-4 51.1>0.9

90.3

6Benzothiazole, 2-(methylthio)-

Industry 615-22-5 65.0>0.9

90.02

7 Eudesmol Medicine 473-15-4 79.7>0.9

92.7

8 Diazinone Pesticide 333-41-5 68.4>0.9

90.2

9 Hexylcinnamaldehyde Flavor 101-86-0 68.4>0.9

91.1

10 TCIPPFlame retardant

13674-84-5

72.2>0.9

90.7

11 Benzyl Benzoate Medicine 120-51-4 61.3>0.9

90.2

12 Dihydrochalcone Flavor 1083-30-3 79.9>0.9

90.5

13 Dimethenamid Pesticide87674-68-

862.0

>0.99

< 0.01

14 Prometryn Pesticide 7287-19-6 62.6>0.9

90.02

15 Malathion Pesticide 121-75-5 54.2>0.9

90.01

6

16 Musk ketone PPCP 81-14-1 55.5>0.9

9< 0.01

17 Anthraquinone Industry 84-65-1 56.4>0.9

90.6

18 Pretilachlor Pesticide51218-49-

697.8

>0.99

0.2

19 di-p-Tolyl sulfone Industry 599-66-6 96.8>0.9

90.01

20 Hexaconazole Pesticide79983-71-

4122.7

>0.99

0.1

21 Fudiolan Pesticide50512-35-

1108.8

>0.99

0.02

22 TDCPPFlame retardant

13674-87-8

65.2>0.9

90.8

23 TBEP Plasticizer 78-51-3 76.5>0.9

93.0

24 Diethylhexyl adipate Plasticizer 103-23-1 87.7>0.9

90.5

25 Bromopropylate Pesticide18181-80-

192.3

>0.99

0.02

26 Mefenacet Pesticide73250-68-

771.4

>0.99

1.5

27 Ipconazole Pesticide125225-

28-777.6

>0.99

0.6

7

Table S-3. Comparison of the number of peaks found in the 50 samples with normal nontarget screening and nontarget screening with deconvolution (multiple libraries were included for the library search).

Normal nontarget

screening (A)

Nontarget

screening with

deconvolution (B)

Ratio (B/A)

Total Peaks 87,000 705,000* 8.1

Peaks with MF ≧ 900 326 1161 3.6

Peaks with levels 1–3 in

the level system 244 722 3

Assigned peaks (levels

1 and 2 in level system) 30 106 3.5

See Table S-1 for details regarding the definition of level system.*Less sensitive peak picking was performed in this process**“Accidental match,” which is a library match with few spectra (<30) in the library data or test data, was observed in peaks with MF ≧ 900.

8

Figure S-3. Identified compounds from GC GC–HRTOFMS data with normal nontarget screening (levels 1–3).See Table S-1 for the details of definition of level system.

9

Figure S-4. Spatial distribution of detected compounds by nontarget screening except for alky chain-based compounds (levels 1–3). a) Without deconvolution process. b) With deconvolution process.Compounds detected in the procedural blank have been removed in both cases.

10

Figure S-5. Spatial patterns of the concentration for detected compounds (level 1). a) Pretilachlor (Pesticide), b) TCIPP (Flame retardant), c) Benzyl Benzoate (Medicine etc.), and d) Musk Ketone (PPCP)

11

Figure S-6. Spatial patterns of all the detected compounds (level 1).Industries (Tetramethyl decynediol, di-p-tolyl sulfone, Anthraquinone, Diethylhexyl adipate, Benzothiazole, 2-(methylthio)-), Flavors/Fragrance (Hexylcinnamaldehyde, Dihydrochalcone), PPCPs (Musk ketone, Hedione, Azulol), Medicines (Benzyl Benzoate, Eudesmol), Pesticides (Diphenylamine, Diazinone, Dimethenamid, Prometryn, Malathion, Pretilachlor, Hexaconazole, Fudiolan, Bromopropylate, Mefenacet, Ipconazole), Flame retardants (TDCPP, TCIPP, TBEP), PAH (Iodonaphthalene)

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Reference1. Schymanski, E. L.; Jeon, J.; Gulde, R.; Fenner, K.; Ruff, M.; Singer, H. P.; Hollender, J., Identifying Small Molecules via High Resolution Mass Spectrometry: Communicating Confidence. Environ. Sci. Technol. 2014, 48, (4), 2097-2098.

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