Supporting Information

Supporting Information

Development and Application of a High-Precision Algorithm for

Nontarget Identification of Organohalogens Based on

Ultrahigh-Resolution Mass Spectrometry

Qing-Long Fu

1

_{, Manabu Fujii}

1

_{*, Eunsang Kwon}

2

1

_{Department of Civil and Environmental Engineering, Tokyo Institute of Technology,}

2-12-1,

Ookayama, Meguro-ku, Tokyo 152-8550, Japan.

2

_{Research and Analytical Center for Giant Molecules, Graduate School of Science,}

Tohoku University, 6-3 Aoba, Aramaki, Aoba-Ku, Sendai 980-8578, Japan.

Contents

Content SI1. Theoretical isotopic pattern calculation.

Content SI2. Description of Xn-DBPs formula library for assignment test.

Content SI3. Exemplification of the formula assigning flow for the parent ion m/z0

490.862162 (C

15

H

18

O

9

Br

2

).

Content SI4. Molecular Characteristics of freshwater DOM.

Content SI5. Discussions regard Cl-adducts.

Content SI6 FTICR MS/MS analysis.

Content SI7 Non-halogenated byproducts.

Content SI8. Electrophilic substitution and addition equation for DBP formation.

Content SI9 Halomethane standards for FTICR MS measurement.

Table S1. Xn-DBPs formulae for assignment accuracy evaluation.

Table S2 DOM molecular parameters used for principle component analysis (PCA)

analysis.

Table S3. Criteria of molecular class for molecular formulae categorization.

Table S4. Effect of precursor inspection (the Optional Rule 2) on Cl- and Br-containing

formulae identification for freshwater DOM samples (in the absence of chlorination

treatment).

Table S5. The putative Cl-adducts and their precursor identified in SRNOM and NRNOM.

Table S6. Formula and RA of identified organic halogens and their relevant putative

precursors in the chlorinated SRNOM and seawater samples.

Figure S1. Formula assignment flows for the parent ion m/z0=490.862162 detected in the

chlorinated SRNOM with Br

-

_{. Red arrows indicate the assigning flow run in this study.}

Figure S2. Representative putative Cl-adducts identified in SRNOM and NRNOM.

Figure S3. The van Krevelen diagram of halogenated compounds naturally present in the

freshwater samples before chlorination.

Figure S4. The van Krevelen diagrams of the Tokyo Bay seawater DOM (Odaiba sample)

(A): (1) N-containing saturated compounds+ others, (2) aminosugars+ others, (3)

carbohydrates, (4) unsaturated hydrocarbons, (5) lignins, (6) tannins, (7) condensed

aromatics.

Figure S5. The van Krevelen diagrams of non-halogenated formulae for DOM in the Tama

River (upstream) sample. (1) N-containing saturated compounds+ others, (2)

aminosugars+ others, (3) carbohydrates, (4) unsaturated hydrocarbons, (5) lignins, (6)

tannins, (7) condensed aromatics.

Figure S6. The van Krevelen diagrams of SRNOM compounds before chlorination

treatment. (1) N-containing saturated compounds + others, (2) aminosugars + others, (3)

carbohydrates, (4) unsaturated hydrocarbons, (5) lignins, (6) tannins, (7) condensed

aromatics.

Figure S7. Some typical surfactant peaks in the FTICR MS spectra of Tokyo Bay seawater

DOM (Odaiba sampling station).

Figure S8. The enlarged FTICR MS spectra for the parent and isotopic ions of

C

12

H

19

O

8

Cl

3

(A)

and

the related Cl-adduct ions

(B) detected in the Tokyo Bay Odaiba seawater sample with

the theoretical spectra of sucralose and its Cl-adduct ions illustrated in blue color

(FWHM=0.0038).

Figure S9. Expanded FTICR MS spectra of SRNOM before and after chlorination

treatment at nominal mass 337, 339, and 341. Cl-DBPs parent and daughter peaks are

indicated by the filled and unfilled symbols, respectively.

Figure S10. The expanded FTICR MS spectra of SRNOM before and after chlorination

treatment for C

1

H

2

Br

2

(A), C

2

H

2

O

2

Br

2

(B), and C

7

H

3

O

3

Br

3

(C) ions with theoretical spectra

of in negative mode illustrated in black color (FWHM=0.0038).

Figure S11. The expanded FTICR MS spectra of SRNOM before and after chlorination

for C

10

H

7

O

5

Cl

1

ions with theoretical spectra of in negative mode illustrated in black color

(FWHM=0.0038).

Figure S12. The theoretical FTICR MS spectra of [C1

H

1

Br

2

]

-

, [C

1

Cl

1

Br

2

]

-

, and [C

1

Br

3

]

-ions (FWHM=0.0038), and expanded FTICR MS spectra of 5.0 mg/L halomethane

(dibromomethane

(C

1

H

2

Br

2

)

tribromomethane

(C

1

H

1

Br

3

),

and

dibromomonochloromethane (C

1

H

1

Cl

1

Br

2

)) standards in the presence and presence of ~75

mg-C/L PPFAII.

Figure S13. The van Krevelen diagrams of Cl-DBPs, and Br-DBPs in chlorinated

SRNOMN in without (A) and with (B) bromide, and halogenated (C) compounds in Tokyo

Bay (Odaiba) seawater sample. Note that X = H + Cl + Br in the y-axis for electrophilic

substitution and X = H- Cl - Br in the y-axis and O′=O- Cl - Br in x-axis for electrophilic

addition. Scattered plot size was proportional to RA values.

Figure S14. The mass distribution (A) and van Krevelen diagram (B) for 2,815 known

DBPs formula used in this study. Panel B: X=H + Cl + Br in the y-axis; (1) N-containing

saturated compounds+ others, (2) aminosugars+ others, (3) carbohydrates, (4) unsaturated

hydrocarbons, (5) lignins, (6) tannins, (7) condensed aromatics.

Figure S15. The van Krevelen diagrams for the formulae assigned by the TRFu Code and

the NOMDBP Code: (A) more heteroatoms formulae reassigned to

13

_{C-formulae in the}

NOMDBP Code; (B) heteroatoms-rich yet oxygen deficient formulae from the TRFu Code

were denied or reassigned to formulae with less heteroatoms by the NOMDBP Code and

other discrepancies. Size of scatter plots were proportional to RA values.

Figure S16. FTICR MS/MS fragmentation spectra of the parent ion at m/z 430.98398

([C

12

H

19

O

8

Cl

4

]

-

) and the proposed fragmentation pathway. Dash lines/arrows indicate the

absence of relevant neutral loss fragments.

Content SI1. Theoretical isotopic pattern calculation.

For the molecule C

c

H

h

O

o

N

n

S

s

P

p

Cl

cl

Br

br

, its isotopic pattern contains one monoisotopic

peak and (1+1)×(cl+1)×(br+1)-1 number of

13

C,

37

Cl and/or

81

Br isotopic peaks with their

relative isotopic abundances following the rule of binomial distribution. The isotopic mass

distribution and intensity of isotopic formula, C

c-x13

C

x

H

h

O

o

N

n

S

s-k34

S

k

P

p

Cl

cl-y37

Cl

y

Br

br-z81

Br

z

,

can be calculated from Eq.(S1) and Eq.(S2), respectively, as follows:

1 0 13C 12C 34S 32S 37Cl 35Cl 81Br 79Br

/

/

(

)

(

)

(

)

(

)

m z

m z

x

m

m

k

m

m

y

m

m

z

m

m



 



 



 



 



(S1)

13C 34S 37Cl 81Br 1 0 12C S 35Cl 79Br

C

x_C

(

Abu

)

x

C

_Sk

(

Abu

)

k

C

_cly

(

Abu

)

y

C

z_br

(

Abu

)

z

In

In

Abu

Abu

Abu

Abu



















(S2)

where the parameters, c, x, h, o, n, s, k, p, cl, y, br, and z represent the atom number of

12

_C,

13

_{C, H, O, N,}

32

_S,

34

_{S, P,}

35

_Cl,

37

_Cl,

79

_{Br and}

81

_{Br, respectively. m/z}

0

and In

0

are the m/z

value and intensity of monoisotopic peak, respectively; and m/z

1

and In

1

are the m/z value

and intensity of its isotopic peak, respectively. The parameters, x, k, y, and z are in the

ranges of 0-1, 0-1, 0- cl and 0-br (x+ k+ y+ z ≠ 0), respectively. C

Cx

, C

Sk

, C

cly

and C

brz

are

the binomial coefficient of C, S, Cl and Br isotopologues. Abu

13C

, Abu

12C

, Abu

34S

, Abu

32S

,

Abu

37Cl

, Abu

35Cl

, Abu

81Br

, and Abu

79Br

are the natural abundance of

13

C (1.07%),

12

C

(98.93%),

34

S (4.29%),

32

S (94.93%),

37

Cl (24.22%),

35

Cl (75.78%),

81

Br (49.31%), and

79

_{Br (50.69%), respectively.}

Content SI2. Description of Xn-DBPs formula library for assignment test.

The mass frequency distribution of Xn-DBPs compounds is comparable to that for

NOM UHR-MS spectra with the maximum mass around 400 Da (

Figure S14A

),

1,2

. The

selected chemicals distributed in all the molecular classes of the Van Krevelen diagram

(

Figure S14B

) are mainly categorized into lignins (55.7%), followed by condensed

aromatics (18.4%) and proteins + lipids (17.5%). Totally, there were 2,815 unique parent

formulae (2,303, 471, 33, 6 and 2 for Cl-containing, Br-containing, Cl-and Br-containing,

Cl-and I-containing, and Br-and I-containing formulae, respectively), 4,306

37

Cl and/or

81

_{Br isotopic formulae (labeled as major isotopic formulae), and 7, 277}

13

_{C and/or}

34

_S

isotopic formulae (labeled as minor isotopic formulae) in the Xn-DBP formula library. The

intensity for parent peaks was all set as 1000 in the formula assignment test. All the DBP

peaks (totally 14,398 peaks) were also combined with the FTICR MS spectrum of SRFA

containing 9,753 peaks (as a representative of non- halogenated NOM sample). The

intensity of 14,398 Xn-DBP peaks were normalized with 1,000 and multiplied with one

fifth of the maximum intensity of SRFA peaks to elucidate the possible influence of

non-halogenated NOM peaks on the assignment performance of the NOMDBP Code (to Cl-

and Br-DBPs as well as non-DBPs).

Content SI3. Exemplification of the formula assigning flow for the parent ion m/z0

490.862162.

The running flow of the NOMDBP Code was exemplified in

Figure S1

for the parent

ion m/z0 (490.862162) detected in chlorinated SRNOM with Br

-

_{. Nine solutions containing}

Cl and/or Br were calculated for this parent ion m/z0 under the calculation conditions (1.0

ppm error, Cl≤ 4 and Br≤ 2); and no Cl- or Br-free solution was computed within 1 ppm

error. The formula assignment algorithm worked in different flow for the following

scenarios:

(1) For the scenario of enabling all three optional rules in the calculation conditions,

which was performed in the present study. Then, 6 solutions were denied by the isotopic

pattern inspection. Since 1 or more of the remaining three organohalogens contains

multiple number of Cl+Br, the Optional Rule 1 was automatically skipped. After precursor

inspection, only the solution, C

15

H

10

O

9

Br

2

, was selected due to the presence of putative

precursor, C

15

H

12

O

9

, in the FTICR MS spectrum of chlorinated SRNOM with Br

-

. The

Optional Rule 3 was also skipped as a result of the presence of putative precursor for the

sole solution C

15

H

10

O

9

Br

2

. This sole solution was further examined with the selection rules

(1) - (5) (

Figure 1

), and finally determined for the parent ion m/z0. The isotopic formulae

were assigned to the isotopic ions m/z1 492.860009 and m/z2 494.8557772

(C

15

H

10

O

979

Br

181

Br

1

and C

15

H

10

O

981

Br

2

, respectively) by the isotopic pattern. The

aforementioned running flow of this study was highlighted using red arrows in

Figure S1

.

(2) If all three optional rules in the calculation were disabled, the three solutions

successfully passed isotopic pattern inspection (C

15

H

10

O

9

Br

2

, C

14

H

15

O

4

S

3

Cl

2

Br

1

and

C

8

H

18

O

6

N

2

S

3

Br

2

) were directly examined with the selection rules (1) - (5) (

Figure 1

). The

solution with more Cl+Br, C

14

H

15

O

4

S

3

Cl

2

Br

1

, was finally determined for parent ion m/z0

in

this

case.

And

the

isotopic

formulae

C

14

H

15

O

4

S

335

Cl

281

Br

1

and

C

14

H

15

O

4

S

335

Cl

137

Cl

181

Br

1

were assigned to isotopic ions m/z1 and m/z2, respectively.

(3) For the scenario of disabling the Optional Rule 2, the solutions, C

15

H

10

O

9

Br

2

,

C

14

H

15

O

4

S

3

Cl

2

Br

1

and C

8

H

18

O

6

N

2

S

3

Br

2

, were examined with the selection rules (1) - (5)

(

Figure 1

) because the parent ion m/z0 was newly appeared in the chlorinated SRNOM.

The formulae ultimately assigned to parent and isotopic ions were identical to these in the

second scenario.

Content SI4. Molecular Characteristics of freshwater DOM.

Contrasting to the chlorinated DOM, the UHR-MS spectra of DOM samples (SRFA,

NLFA, PLFA, MRNOM) as well as the SPE-purified SRNOM, NRNOM, and Tama river

DOM samples were analyzed with the NOMDBP Code under similar calculation

conditions (Cl ≤2 and Br ≤2 in this scenario). In accordance with the molecular

compositions of IHSS DOM samples, all identified compounds in Tama River were

dominated by lignin-like (~86% of all intensity) and tannin-like compounds (~6-~7% of

all intensity). While CHO compounds (compounds only containing C, H, and O) were the

predominant class of all freshwater samples (60-93% of all intensities), CHON compounds

(compounds only containing C, H, O, and N) were richer in Tama River (18%-~32% of all

intensity) than these for IHSS DOM (3%-5%). The intensity weighted molecular

characteristics (e.g. O/C

iw

=0.47-0.55; H/C

iw

= 1.01-1.22; DBE

iw

=10.22-14.14) of SRFA,

SRNOM, river water computed by the NOMDBP Code were found to be similar to these

parameters calculated for DOM from headwater stream (O/C

iw

=0.7; H/C

iw

=1.00)

3

, SRFA

(O/C

iw

=0.55, H/C

iw

=1.05, DBE

iw

=10.85)

4

, Taihu Lake (O/C

iw

=0.52-0.54; H/C

iw

=1.21-1.24)

5

_{, Lake Superior and its watershed water (H/C}

iw

= 1.08-1.28, O/C

iw

= 0.38-0.42,

DBE

iw

= 10.8-14.2)

6

, and Amazon Basin river (H/C

iw

=1.01-1.12, O/C

iw

=0.49-0.51,

DBE

iw

= 9.93-11.58 for CHO and CHON compounds)

7

, suggesting the comparable

assignment performance/accuracy of the NOMDBP Code for DOM samples prior to the

chlorination treatment. However, after running precursors inspection, the assignment

performance of the NOMDBP Code differentiated slightly from our open TRFu Code

8

.

For example, both two codes shared ~93% identical formulae (8,551 of 9,203 peaks) for

SRFA. Compared with the TRFu Code, the previously proposed m/z-dependent error for

the

13

C-

12

C mass difference

8

are incorporated in the NOMDBP Code. This update in

NOMDBP code was capable of assigning additional 634 peaks to

13

C-formulae that

contained less heteroatoms and located in the central area of the van Krevelen diagram

(

Figure S15A

). As illustrated in

Figure S15B

, heteroatoms-rich yet oxygen deficient

formulae (e.g. H/C>1 and O/C<0.5) were excluded or reassigned by the rule of heteroatom

less than O (N+S+P<O) in the NOMDBP Code, which accounted for ~17% (132 peaks) of

all differently assigned formulae. The remaining discrepancy (25 of 784 peaks) are caused

by the minor changes in the functions (e.g. the strict

13

_{C isotopic pattern) used in the}

NOMDBP Code.

Content SI5. Discussions regard Cl-adducts.

While suspicious halogens could be eliminated by the optional precursor inspection

rule (i.e., Filter Rule 3), the identification of Cl-halogens can be affected by Cl-adduct ions

potentially formed during the ESI negative mode ionization via interaction of DOM

molecules and remaining Cl

-

from the SPE-extraction using HCl

27

. In this study, the

potential adduct of Cl-molecules were observed for the SPE-extracted SRNOM and

NRNOM, while not for the SPE-extracted SRFAII (

Figure. S2

). These results suggest that

the formation of Cl-DOM adducts is controlled not only by the presence of remaining Cl

-

,

but also by the types of DOM. In order to avoid adduct formation, formic acid has been

suggested in the SPE extraction instead of HCl

16-18,27,28

. However, the employment of other

type of acid, formic acid, in SPE extraction (instead of HCl) may lead to the occurrence of

formate adduct ions in ESI negative mode

29-31

, interfering the formula assignment of

non-halogenated DOM molecules. Therefore, an additional SPE cartridges washing with

ultrapure water is alternatively suggested to completely remove remaining Cl

-

_{or formate}

ions in the case of simultaneously analyzing halogenated and non-halogenated DOM

compounds. However, the neutral (or slightly acidic) ultrapure water may also lead to the

loss of a part of the DOM sorbed on SPE. Because rigorous formula assignments are central

in X-DBPs characterization, only the X-DBPs formulae treated with precursor inspection

(Filter Rule 2) were discussed for freshwater DOM in the following sections.

Content SI6 FTICR MS/MS analysis.

For further identification of organohalogens in the Tokyo Bay seawater, parent ions of

seawater DOM ions at the nominal mass of 431 (2 Da mass windows for ion isolation)

were fragmented in the quadrupole via collision induced dissociation with argon gas. The

fragmentation spectra were recorded in the same FTCR MS instrument with 100 scans, 2

MWord data size, 15.0 V collision voltage, and 1 s ion accumulation time.

As depicted in

Figure S16

, the parent ion at m/z 430.98398 ([M+Cl]

-

) was observed to

continuously lose two HCl, yielding two conspicuous fragment ions at m/z 395.0073 and

359.03065 ([M-HCl]

-

and [M-2HCl]

-

, respectively). While typical NOM fragment ions are

formed via CO

2

, CO and/or H

2

O release from parent ions in the MS/MS spectra

9-11

, these

fragments were not identified for the parent ion m/z 430.98398, suggesting the absence of

acidic (e.g., carboxyl) functional group in the structure of the parent ion. The attached Cl

is loosely bound to precursors, which is in contrast to Cl directly bound to carbon skeletons.

The approximately ten times higher ion intensity of [M-HCl]

-

_{that for the [M-2HCl]}

-

_ion,

therefore, suggests that the ion at m/z 430.983997 ([C

12

H

19

O

8

Cl

3

+Cl]

-

) is the Cl-adduct ion

of neutral sucralose (an artificial sweetener, C

12

H

19

O

8

Cl

3

) in the Tokyo Bay seawater DOM.

The dominant loss of one HCl for the ion 3 originated from the Cl and ortho-hydroxyl

directly bound to the oxane moiety of sucralose. The fragmentation pathway of the parent

ion m/z 430.983997 was illustrated in Figure S16.

Content SI7 Non-halogenated byproducts.

Non-halogenated byproducts are often formed during the disinfection treatment,

revealing the mechanism of Xn-DBPs formation

29,39,40

. In addition to non-halogenated

byproducts with low molecular weights detected with conventional chromatographic and

mass techniques, the NOMDBP Code is capable of simultaneously assigning formulae to

non-halogenated byproducts with larger molecular weights in the FTCR MS spectra.

Totally, 102 and 243 newly formed and chlorination-derived putative non-halogenated

byproducts were identified in this study (

Table S7

), including two reported

non-halogenated byproducts, C

8

H

6

O

4

and C

8

H

6

O

5

, decomposed from Xn-DBPs

29

. The newly

formed C

8

H

6

O

5

was absent in non-chlorinated SRNOM. In case of C

8

H

6

O

4

, the peak for

this molecule was detected in non-chlorinated SRNOM, the chlorination treatment showed

substantially high RA in both “ClO

-

” and “ClO

-

+Br

-

” treatments (e.g., by 2.7 and 3.6 folds,

respectively). Therefore, the comparison of formulae results exported from the NOMDBP

Code for chlorinated and non-chlorinated samples provides additional information in

elucidating the formation and transformation of halogenated and non-halogenated products

during disinfection process.

Content SI8. Electrophilic substitution and addition equation for DBP formation.

Both electrophilic substitution and electrophilic addition are considered to inspect

DBP-precursors (the Optional Filter Rule 2) using Equation (S3) and (S4), respectively:

2

C H O N S P

_{c h o n s p}



x

HOX



C H

_{c h x}

O

_o

N S

_{n s}

P

_p

X

_x



x

H

O

(S3)

C H O N S P

_{c h o n s p}



x

HOX



C

_c

H

_{h x}

O

_ox

N

_n

S P

_{s p}

X

_x

(S4)

where c, h, o, n, s, and p are the number of C, H, O, N, S, and P atom in DBP-precursors;

and x is the number of hypochlorous acid and or hypobromous acid involved in DBP

formation.

Content SI9 Halomethane standards for FTICR MS measurement.

Three halomethane (dibromomethane (C

1

H

2

Br

2

) tribromomethane (C

1

H

1

Br

3

), and

dibromomonochloromethane (C

1

H

1

Cl

1

Br

2

)) standard stock solutions (≥99% purity) were

purchased from Kanto Chemical Co. Inc., Japan. The 5 mg/L Halomethane standard

solutions were diluted individually by 50% methanol for FTICR MS measurement.

Additionally, the ~75 mg-C/L Pahokee Peat II standard fluvic acid (PPFAII, 2S103F

purchased from IHSS) was mixed with halomethane mixtures (5.0 mg/L for each

halomethane species) in 50% methanol was also measured to examine the effects of NOM

molecules on the ionization and defection of halomethanes by FTICR MS.

All standard samples were measured by the Bruker SolariX 9.4T FTCR MS in negative

ion mode with the instrument conditions detailed in Section 2.3 except for ion accumulation

time. The ion accumulation for halomethane standards was 0.3, 0.3 and 0.5 for C

1

H

2

Br

2

,

C

1

H

1

Br

3

, and C

1

H

1

Cl

1

Br

2

, respectively and 0.07 s for all halomethane standards in the

presence of ~75 mg-C/L NOM (PPFAII).

Table S2 DOM molecular parameters used for principle component analysis (PCA) analysis.

Sample Measured

m/z H/C O/C S/C Cl/C Br/C AImod DBE NOSC X/C

Tama River (upstream) DOM 416.67 1.42 0.42 0.00 0.03 0.03 0.12 5.94 -0.42 1.48 PLFA 569.39 1.45 0.30 0.00 0.00 0.04 0.11 8.63 -0.63 1.49 SRNOM 384.72 1.38 0.41 0.00 0.05 0.01 0.16 6.07 -0.42 1.43 SRNOM+ClO- 383.84 0.88 0.58 0.00 0.06 0.00 0.43 9.41 0.34 0.94 SRNOM+ClO-+Br- 429.21 0.72 0.62 0.00 0.00 0.11 0.52 9.99 0.62 0.83 Seawater DOM 428.78 1.62 0.59 0.00 0.26 0.00 0.02 2.17 -0.17 1.88 NRNOM 381.72 1.39 0.38 0.00 0.06 0.00 0.18 5.95 -0.57 1.45 MRNOM 529.43 1.14 0.51 0.00 0.02 0.03 0.27 9.37 0.05 1.19

Table S3. Criteria of molecular class for molecular formulae categorization.

Molecular class

Criteria

Carbohydrates

H/C: 1.5-2.4; O/C: 0.71-1.2

Aminosugars

H/C: 1.5-2.2; O/C: 0.52-0.71; N>0

N-containing saturated compounds

H/C: 1.5-2.2; O/C: 0-0.52; N>0

Tannins

H/C: 0.5-1.5; O/C: 0.67-1.2

Lignin/ carboxyl- rich acyclic molecules

H/C: 0.7-1.5; O/C: 0.1-0.67

Unsaturated hydrocarbons

H/C: 0.7-1.5; O/C: 0-0.1

Condensed aromatic structures

H/C: 0.2-0.7; O/C: 0-0.67

Others

Formula beyond above criteria

Table S4. Effect of precursor inspection (the Optional Rule 2) on Cl- and Br-containing

formulae identification for freshwater DOM samples (in the absence of chlorination

treatment).

DOM samples

Precursor inspection (Optional Rule 2) unexecuted

Precursor inspection (Optional Rule 2) executed Cl-formula number Br-formula number Intensity percentage 1) Cl-formula number Br-formula number Intensity percentage 1) SRFA 8 20 0.11% 0 0 0.00% SRFAII 2) _{7 107 0.45% 0 0 0.00%} NLFA 8 22 0.11% 0 0 0.00% PLFA 17 267 3.22% 0 11 0.06% SRNOM 2) _{46 106 0.45% 32 34 0.14%} NRNOM 2) _{140 77 1.21% 114 0 0.80%} MRNOM 23 153 1.11% 2 4 0.03% Tama River (downstream) DOM 26 22 0.55% 0 0 0.00% Tama River (upstream) DOM 10 76 0.29% 2 2 0.01%

1) Percentage of intensity for halogenated formulae relative to total intensity. 2) NOM samples were subjected to the SPE-extraction using HCl.

Table S5. The putative Cl-adducts and their precursor identified in SRNOM and NRNOM.

Precursor 35_Cl-adduct 37_Cl-adduct

m/z Formula Error (ppm) RA m/z Formula Error (ppm) RA m/z Formula Error (ppm) RA SRNOM 295.118735 C15H20O6 0.08 42.08 331.095428 C15H20O635Cl1 0.12 5.39 333.092590 C15H20O637Cl1 0.45 1.88 307.118720 C16H20O6 0.03 29.09 343.095502 C16H20O635Cl1 0.33 3.21 345.092402 C16H20O637Cl1 -0.11 1.23 311.113645 C15H20O7 0.06 69.52 347.090279 C15H20O735Cl1 -0.07 6.11 349.087353 C15H20O737Cl1 0.00 2.29 321.134374 C17H22O6 0.04 28.01 357.111141 C17H22O635Cl1 0.29 3.88 359.107864 C17H22O637Cl1 -0.63 1.41 323.113645 C16H20O7 0.06 58.57 359.090357 C16H20O735Cl1 0.15 5.93 361.087488 C16H20O737Cl1 0.38 1.95 323.150017 C17H24O6 0.02 22.69 359.126762 C17H24O635Cl1 0.20 4.14 361.123619 C17H24O637Cl1 -0.33 1.37 325.129272 C16H22O7 -0.01 55.56 361.105974 C16H22O735Cl1 0.06 6.09 363.103275 C16H22O737Cl1 0.75 2.26 335.150021 C18H24O6 0.03 27.55 371.126753 C18H24O635Cl1 0.17 5.37 373.123583 C18H24O637Cl1 -0.42 1.84 337.129269 C17H22O7 -0.02 61.14 373.105999 C17H22O735Cl1 0.12 6.96 375.102987 C17H22O737Cl1 -0.04 2.08 349.165643 C19H26O6 -0.05 21.55 385.142467 C19H26O635Cl1 0.33 4.83 387.139435 C19H26O637Cl1 0.12 1.59 351.144885 C18H24O7 -0.12 55.89 387.121627 C18H24O735Cl1 0.06 7.80 389.118488 C18H24O737Cl1 -0.42 2.28 379.139792 C19H24O8 -0.13 80.97 415.116649 C19H24O835Cl1 0.32 8.64 417.113285 C19H24O837Cl1 -0.68 2.49 NRNOM 267.123817 C14H20O5 0.08 13.54 303.100466 C14H20O535Cl1 -0.03 3.24 305.097698 C14H20O537Cl1 0.57 1.14 279.123805 C15H20O5 0.03 20.80 315.100479 C15H20O535Cl1 0.02 4.40 317.097675 C15H20O537Cl1 0.48 1.35 281.103077 C14H18O6 0.06 41.12 317.079757 C14H18O635Cl1 0.06 4.34 319.076776 C14H18O637Cl1 -0.04 1.36 281.139463 C15H22O5 0.06 17.14 317.116146 C15H22O535Cl1 0.07 4.72 319.113277 C15H22O537Cl1 0.32 1.65

283.118715 C14H20O6 0.01 35.20 319.09539 C14H20O635Cl1 0.00 6.53 321.092504 C14H20O637Cl1 0.20 2.05 291.087403 C15H16O6 -0.03 19.32 327.064276 C15H16O635Cl1 0.57 1.93 329.061056 C15H16O637Cl1 -0.25 0.80 293.103071 C15H18O6 0.03 38.64 329.079797 C15H18O635Cl1 0.18 4.31 331.076592 C15H18O637Cl1 -0.59 1.48 293.139444 C16H22O5 -0.01 11.69 329.116227 C16H22O535Cl1 0.31 2.50 331.113215 C16H22O537Cl1 0.12 0.99 295.118706 C15H20O6 -0.02 54.89 331.095374 C15H20O635Cl1 -0.04 8.92 333.092377 C15H20O637Cl1 -0.19 3.12 297.097959 C14H18O7 -0.06 64.25 333.074627 C14H18O735Cl1 -0.08 6.05 335.071830 C14H18O737Cl1 0.38 2.42 297.134334 C15H22O6 -0.09 38.68 333.111036 C15H22O635Cl1 -0.01 8.09 335.108181 C15H22O637Cl1 0.28 2.43 307.118693 C16H20O6 -0.06 33.09 343.095487 C16H20O635Cl1 0.29 4.88 345.092418 C16H20O637Cl1 -0.06 1.58 309.097964 C15H18O7 -0.04 67.55 345.074639 C15H18O735Cl1 -0.04 6.06 347.071748 C15H18O737Cl1 0.13 1.84 309.134346 C16H22O6 -0.05 35.51 345.111034 C16H22O635Cl1 -0.01 7.26 347.108037 C16H22O637Cl1 -0.15 2.39 311.113614 C15H20O7 -0.04 84.83 347.090257 C15H20O735Cl1 -0.13 9.39 349.087329 C15H20O737Cl1 -0.07 3.24 321.134357 C17H22O6 -0.01 32.44 357.111052 C17H22O635Cl1 0.04 7.03 359.107843 C17H22O637Cl1 -0.68 2.17 323.113611 C16H20O7 -0.05 65.27 359.090277 C16H20O735Cl1 -0.07 9.16 361.087394 C16H20O737Cl1 0.11 2.75 323.149989 C17H24O6 -0.07 28.89 359.126695 C17H24O635Cl1 0.02 8.51 361.123661 C17H24O637Cl1 -0.22 2.46 325.129235 C16H22O7 -0.13 62.46 361.105931 C16H22O735Cl1 -0.06 10.73 363.103172 C16H22O737Cl1 0.46 3.28 335.113584 C17H20O7 -0.12 50.07 371.090334 C17H20O735Cl1 0.08 6.21 373.087024 C17H20O737Cl1 -0.88 1.74 335.149981 C18H24O6 -0.09 31.51 371.126689 C18H24O635Cl1 0.00 6.96 373.123508 C18H24O637Cl1 -0.62 2.39 337.129248 C17H22O7 -0.08 69.06 373.105937 C17H22O735Cl1 -0.04 10.56 375.103027 C17H22O737Cl1 0.06 3.26 337.165619 C18H26O6 -0.12 23.84 373.142332 C18H26O635Cl1 -0.02 7.57 375.139277 C18H26O637Cl1 -0.30 2.09 339.144894 C17H24O7 -0.09 55.85 375.121574 C17H24O735Cl1 -0.08 10.54 377.118684 C17H24O737Cl1 0.08 3.43 349.129212 C18H22O7 -0.18 54.72 385.105959 C18H22O735Cl1 0.01 9.24 387.102800 C18H22O737Cl1 -0.53 2.76

349.165606 C19H26O6 -0.16 25.23 385.142367 C19H26O635Cl1 0.07 10.46 387.139277 C19H26O637Cl1 -0.29 3.25 351.108499 C17H20O8 -0.12 78.88 387.085237 C17H20O835Cl1 0.05 7.04 389.082643 C17H20O837Cl1 0.96 2.25 351.144869 C18H24O7 -0.16 63.78 387.121602 C18H24O735Cl1 0.00 13.84 389.118533 C18H24O737Cl1 -0.31 3.71 351.181259 C19H28O6 -0.15 18.18 387.157953 C19H28O635Cl1 -0.09 10.16 389.154714 C19H28O637Cl1 -0.83 2.85 363.144885 C19H24O7 -0.11 59.98 399.121735 C19H24O735Cl1 0.33 11.52 401.118495 C19H24O737Cl1 -0.39 4.03 363.181236 C20H28O6 -0.21 18.78 399.158011 C20H28O635Cl1 0.06 7.70 401.154702 C20H28O637Cl1 -0.84 2.23 365.124134 C18H22O8 -0.15 90.81 401.100914 C18H22O835Cl1 0.11 9.76 403.097567 C18H22O837Cl1 -0.87 2.66 365.160503 C19H26O7 -0.20 58.29 401.13728 C19H26O735Cl1 0.07 15.70 403.134226 C19H26O737Cl1 -0.19 4.71 365.196927 C20H30O6 -0.09 13.29 401.173657 C20H30O635Cl1 0.05 7.18 403.170520 C20H30O637Cl1 -0.42 2.23 377.160502 C20H26O7 -0.20 43.47 413.137236 C20H26O735Cl1 -0.04 11.81 415.134034 C20H26O737Cl1 -0.65 3.63 379.139786 C19H24O8 -0.14 89.98 415.116558 C19H24O835Cl1 0.10 15.70 417.113517 C19H24O837Cl1 -0.12 4.95 379.176159 C20H28O7 -0.18 39.79 415.152957 C20H28O735Cl1 0.13 15.39 417.149804 C20H28O737Cl1 -0.36 4.56 391.176167 C21H28O7 -0.15 29.08 427.152943 C21H28O735Cl1 0.09 10.34 429.149525 C21H28O737Cl1 -1.00 2.68 393.155439 C20H26O8 -0.13 74.76 429.13226 C20H26O835Cl1 0.21 15.69 431.128893 C20H26O837Cl1 -0.75 3.92 419.171134 C22H28O8 -0.02 44.12 455.148173 C22H28O835Cl1 0.78 10.82 457.144737 C22H28O837Cl1 -0.29 2.89

Table S6. Formula and relative abundance (RA) of identified organic halogens and their

relevant putative precursors in the chlorinated SRNOM and seawater samples.

Putative precursor Organic Cl/Br compounds

NO. Measured

m/z Formula RA Error

Measured

m/z Formula RA Error

Chlorinated SRNOM in the absence of Br

-1 221.009220 C10H6O6 3.97 0.27 254.970128 C10H5O6Cl1 1.91 -0.24 2 223.024824 C10H8O6 5.44 0.06 256.985794 C10H7O6Cl1 3.09 -0.17 3 237.040440 C11H10O6 7.76 -0.09 271.001553 C11H9O6Cl1 3.12 0.24 4 239.056089 C11H12O6 7.87 -0.09 273.017104 C11H11O6Cl1 2.27 -0.13 5 241.035341 C10H10O7 6.41 -0.14 274.996314 C10H9O7Cl1 2.13 -0.33 6 247.024777 C12H8O6 6.60 -0.14 280.985826 C12H7O6Cl1 3.08 -0.05 7 249.004043 C11H6O7 4.60 -0.13 282.965034 C11H5O7Cl1 1.94 -0.25 8 249.040420 C12H10O6 9.56 -0.17 283.001532 C12H9O6Cl1 3.25 0.15 9 251.019681 C11H8O7 9.39 -0.18 284.980787 C11H7O7Cl1 3.49 0.12 10 251.056078 C12H12O6 10.10 -0.13 285.017162 C12H11O6Cl1 3.18 0.08 11 253.035342 C11H10O7 8.97 -0.13 286.996468 C11H9O7Cl1 3.89 0.23 12 255.050993 C11H12O7 11.24 -0.13 289.012050 C11H11O7Cl1 3.50 -0.01 13 261.040446 C13H10O6 8.67 -0.06 295.001514 C13H9O6Cl1 3.95 0.09 14 263.019714 C12H8O7 9.23 -0.04 296.980770 C12H7O7Cl1 3.81 0.06 15 265.035360 C12H10O7 13.12 -0.06 298.996425 C12H9O7Cl1 5.26 0.07 16 265.071736 C13H14O6 12.04 -0.09 299.032815 C13H13O6Cl1 3.50 0.09 17 267.014607 C11H8O8 9.64 -0.12 300.975670 C11H7O8Cl1 3.47 0.01 18 267.051014 C12H12O7 14.54 -0.04 301.012071 C12H11O7Cl1 5.17 0.06 19 267.087402 C13H16O6 19.40 -0.03 301.048403 C13H15O6Cl1 2.89 -0.12 20 269.066670 C12H14O7 21.11 -0.02 303.027687 C12H13O7Cl 4.35 -0.05 21 271.045944 C11H12O8 13.63 0.01 305.006937 C11H11O8Cl1 3.46 -0.10 22 271.082330 C12H16O7 22.40 0.02 305.043413 C12H15O7Cl1 2.74 0.20 23 273.040482 C14H10O6 6.83 0.08 307.001493 C14H9O6Cl1 2.94 0.01 24 275.019719 C13H8O7 7.81 -0.02 308.980788 C13H7O7Cl1 3.34 0.11 25 275.056141 C14H12O6 10.94 0.11 309.017138 C14H11O6Cl1 3.78 0.00

26 277.035387 C13H10O7 14.01 0.04 310.996416 C13H9O7Cl1 5.85 0.04 27 279.014635 C12H8O8 11.76 -0.02 312.975621 C12H7O8Cl1 3.58 -0.15 28 279.051019 C13H12O7 17.81 -0.02 313.012050 C13H11O7Cl1 6.60 -0.01 29 279.087407 C14H16O6 18.97 -0.01 313.048485 C14H15O6Cl1 3.39 0.15 30 281.030273 C12H10O8 16.99 -0.06 314.991321 C12H9O8Cl1 6.04 0.01 31 281.066686 C13H14O7 24.58 0.04 315.027733 C13H13O7Cl1 6.35 0.09 32 281.103078 C14H18O6 30.27 0.06 315.064198 C14H17O6Cl1 3.46 0.35 33 283.045936 C12H12O8 21.28 -0.02 317.006931 C12H11O8Cl1 5.78 -0.12 34 283.082328 C13H16O7 37.44 0.01 317.043365 C13H15O7Cl1 4.79 0.04 35 283.118740 C14H20O6 27.38 0.10 317.079788 C14H19O6Cl1 3.26 0.16 36 285.061599 C12H14O8 30.70 0.03 319.022599 C12H13O8Cl1 4.59 -0.06 37 289.035377 C14H10O7 12.33 0.00 322.996443 C14H9O7Cl1 4.69 0.12 38 289.071770 C15H14O6 11.01 0.03 323.032822 C15H13O6Cl1 2.64 0.10 39 291.014670 C13H8O8 10.80 0.10 324.975705 C13H7O8Cl1 3.99 0.11 40 291.051043 C14H12O7 17.86 0.06 325.012024 C14H11O7Cl1 5.73 -0.09 41 291.087396 C15H16O6 15.73 -0.05 325.048526 C15H15O6Cl1 3.14 0.27 42 293.030287 C13H10O8 19.54 -0.01 326.991305 C13H9O8Cl1 6.50 -0.04 43 293.066692 C14H14O7 22.72 0.06 327.027689 C14H13O7Cl1 6.44 -0.04 44 293.103079 C15H18O6 26.51 0.06 327.064169 C15H17O6Cl1 3.77 0.25 45 295.045928 C13H12O8 25.74 -0.04 329.006957 C13H11O8Cl1 8.60 -0.03 46 295.082333 C14H16O7 37.54 0.02 329.043353 C14H15O7Cl1 6.24 0.00 47 295.118722 C15H20O6 40.69 0.04 329.079929 C15H19O6Cl1 3.98 0.58 48 297.025207 C12H10O9 13.16 0.01 330.986211 C12H9O9Cl1 4.41 -0.07 49 297.061598 C13H14O8 38.76 0.03 331.022593 C13H13O8Cl1 7.39 -0.08 50 297.097966 C14H18O7 54.68 -0.03 331.059018 C14H17O7Cl1 5.51 0.04 51 297.134346 C15H22O6 28.06 -0.05 331.095442 C15H21O6Cl1 5.53 0.16 52 299.040853 C12H12O9 23.19 -0.01 333.001815 C12H11O9Cl1 4.91 -0.20 53 299.077222 C13H16O8 52.82 -0.06 333.038257 C13H15O8Cl1 5.57 -0.03 54 303.051019 C15H12O7 15.21 -0.02 337.012124 C15H11O7Cl1 4.46 0.21 55 303.087401 C16H16O6 10.73 -0.03 337.048586 C16H15O6Cl1 2.80 0.44 56 305.030296 C14H10O8 18.32 0.02 338.991307 C14H9O8Cl1 5.86 -0.03 57 305.066659 C15H14O7 21.00 -0.05 339.027674 C15H13O7Cl1 5.90 -0.09 58 305.103062 C16H18O6 16.53 0.00 339.064223 C16H17O6Cl1 3.06 0.40

59 307.009558 C13H8O9 11.09 0.01 340.970562 C13H7O9Cl1 2.80 -0.06 60 307.045941 C14H12O8 27.86 0.00 341.006938 C14H11O8Cl1 9.75 -0.09 61 307.082331 C15H16O7 28.90 0.02 341.043391 C15H15O7Cl1 5.79 0.11 62 307.118722 C16H20O6 26.41 0.04 341.079863 C16H19O6Cl1 3.22 0.36 63 309.025190 C13H10O9 22.49 -0.05 342.986190 C13H9O9Cl1 6.44 -0.12 64 309.061583 C14H14O8 37.03 -0.02 343.022598 C14H13O8Cl1 8.71 -0.06 65 309.097984 C15H18O7 53.30 0.03 343.059061 C15H17O7Cl1 5.64 0.17 66 309.134356 C16H22O6 29.92 -0.02 343.095478 C16H21O6Cl1 3.65 0.26 67 311.040842 C13H12O9 32.05 -0.04 345.001854 C13H11O9Cl1 8.32 -0.08 68 311.077234 C14H16O8 57.79 -0.02 345.038239 C14H15O8Cl1 7.47 -0.08 69 311.113633 C15H20O7 68.70 0.02 345.074708 C15H19O7Cl1 6.23 0.16 70 313.056519 C13H14O9 47.84 0.05 347.017521 C13H13O9Cl1 8.14 -0.03 71 313.092882 C14H18O8 70.06 -0.03 347.053942 C14H17O8Cl1 5.55 0.07 72 313.129285 C15H22O7 38.58 0.03 347.090297 C15H21O7Cl1 6.27 -0.02 73 315.051031 C16H12O7 11.44 0.02 349.012076 C16H11O7Cl1 3.76 0.06 74 317.030292 C15H10O8 14.69 0.01 350.991250 C15H9O8Cl1 5.46 -0.19 75 317.066666 C16H14O7 17.36 -0.03 351.027767 C16H13O7Cl1 4.20 0.18 76 319.045941 C15H12O8 24.70 0.00 353.006959 C15H11O8Cl1 7.48 -0.03 77 319.082328 C16H16O7 20.91 0.01 353.043449 C16H15O7Cl1 4.65 0.27 78 321.025186 C14H10O9 21.48 -0.06 354.986208 C14H9O9Cl1 6.12 -0.07 79 321.061594 C15H14O8 33.98 0.01 355.022588 C15H13O8Cl1 9.30 -0.08 80 321.097968 C16H18O7 32.06 -0.02 355.059114 C16H17O7Cl1 4.88 0.31 81 323.040842 C14H12O9 35.87 -0.04 357.001881 C14H11O9Cl1 10.23 0.00 82 323.077233 C15H16O8 47.75 -0.02 357.038260 C15H15O8Cl1 8.50 -0.02 83 323.150003 C17H24O6 22.09 -0.03 357.111177 C17H23O6Cl1 4.23 0.39 84 325.020104 C13H10O10 17.63 -0.05 358.981024 C13H9O10Cl1 3.66 -0.34 85 325.056488 C14H14O9 53.02 -0.05 359.017510 C14H13O9Cl1 10.50 -0.06 86 325.092878 C15H18O8 79.13 -0.04 359.053932 C15H17O8Cl1 7.78 0.04 87 325.129264 C16H22O7 53.80 -0.04 359.090359 C16H21O7Cl1 6.18 0.15 88 327.072139 C14H16O9 72.74 -0.05 361.033147 C14H15O9Cl1 8.28 -0.10 89 331.045934 C16H12O8 20.00 -0.02 365.006917 C16H11O8Cl1 5.82 -0.14 90 333.025178 C15H10O9 19.34 -0.08 366.986232 C15H9O9Cl1 5.82 0.00 91 333.061572 C16H14O8 29.64 -0.05 367.022629 C16H13O8Cl1 7.98 0.03

92 335.040830 C15H12O9 35.66 -0.07 369.001824 C15H11O9Cl1 9.67 -0.16 93 335.077242 C16H16O8 38.70 0.01 369.038303 C16H15O8Cl1 8.47 0.09 94 337.020096 C14H10O10 22.63 -0.07 370.981123 C14H9O10Cl1 4.97 -0.07 95 337.056496 C15H14O9 50.90 -0.03 371.017454 C15H13O9Cl1 12.82 -0.21 96 337.092876 C16H18O8 58.53 -0.04 371.053867 C16H17O8Cl1 7.04 -0.14 97 337.165651 C18H26O6 16.74 -0.03 371.126806 C18H25O6Cl1 4.76 0.32 98 339.035762 C14H12O10 40.16 -0.02 372.996701 C14H11O10Cl1 9.44 -0.26 99 339.072135 C15H16O9 72.76 -0.06 373.033150 C15H15O9Cl1 10.84 -0.09 100 339.108521 C16H20O8 85.72 -0.06 373.069587 C16H19O8Cl1 7.00 0.05 101 341.087791 C15H18O9 94.69 -0.04 375.048804 C15H17O9Cl1 8.21 -0.08 102 349.056463 C16H14O9 44.93 -0.12 383.017468 C16H13O9Cl1 11.13 -0.17 103 349.092870 C17H18O8 40.32 -0.06 383.053913 C17H17O8Cl1 7.00 -0.01 104 351.035737 C15H12O10 42.69 -0.09 384.996741 C15H11O10Cl1 10.81 -0.15 105 351.072107 C16H16O9 57.36 -0.14 385.033154 C16H15O9Cl1 11.65 -0.07 106 351.108512 C17H20O8 65.85 -0.08 385.069684 C17H19O8Cl1 7.38 0.30 107 353.051398 C15H14O10 66.04 -0.06 387.012349 C15H13O10Cl1 13.48 -0.25 108 353.087769 C16H18O9 81.10 -0.10 387.048807 C16H17O9Cl1 9.33 -0.07 109 353.124153 C17H22O8 85.71 -0.11 387.085247 C17H21O8Cl1 7.53 0.07 110 353.160545 C18H26O7 32.27 -0.09 387.121652 C18H25O7Cl1 7.72 0.13 111 355.067043 C15H16O10 88.08 -0.07 389.028050 C15H15O10Cl1 10.96 -0.12 112 359.040801 C17H12O9 22.68 -0.15 393.001859 C17H11O9Cl1 5.71 -0.06 113 361.056457 C17H14O9 35.58 -0.13 395.017519 C17H13O9Cl1 9.32 -0.03 114 363.035731 C16H12O10 38.74 -0.11 396.996722 C16H11O10Cl1 9.78 -0.19 115 363.072123 C17H16O9 45.93 -0.09 397.033169 C17H15O9Cl1 10.10 -0.03 116 365.051388 C16H14O10 59.40 -0.09 399.012380 C16H13O10Cl1 14.39 -0.17 117 365.087745 C17H18O9 58.21 -0.16 399.048778 C17H17O9Cl1 9.49 -0.14 118 367.030645 C15H12O11 38.11 -0.11 400.991680 C15H11O11Cl1 8.13 -0.08 119 367.067035 C16H16O10 77.96 -0.09 401.028033 C16H15O10Cl1 14.13 -0.16 120 367.139807 C18H24O8 77.90 -0.09 401.100966 C18H23O8Cl1 8.16 0.24 121 375.035721 C17H12O10 31.08 -0.13 408.996764 C17H11O10Cl1 8.59 -0.08 122 377.051335 C17H14O10 52.46 -0.22 411.012402 C17H13O10Cl1 12.57 -0.11 123 379.030627 C16H12O11 39.52 -0.15 412.991786 C16H11O11Cl1 9.13 0.18 124 379.067011 C17H16O10 66.40 -0.15 413.028083 C17H15O10Cl1 14.07 -0.03

125 381.046265 C16H14O11 66.58 -0.18 415.007342 C16H13O11Cl1 14.49 -0.05 126 391.030630 C17H12O11 35.31 -0.14 424.991766 C17H11O11Cl1 9.04 0.13 127 391.066988 C18H16O10 52.33 -0.21 425.028157 C18H15O10Cl1 12.54 0.14 128 393.046272 C17H14O11 62.06 -0.16 427.007373 C17H13O11Cl1 15.39 0.03 129 393.082653 C18H18O10 61.72 -0.17 427.043941 C18H17O10Cl1 12.18 0.45 130 395.061910 C17H16O11 82.49 -0.19 429.023055 C17H15O11Cl1 16.67 0.10 131 401.051377 C19H14O10 26.58 -0.11 435.012649 C19H13O10Cl1 8.19 0.46 132 403.067035 C19H16O10 39.87 -0.09 437.028154 C19H15O10Cl1 9.85 0.13 133 405.046302 C18H14O11 52.94 -0.08 439.007434 C18H13O11Cl1 13.31 0.16 134 407.061950 C18H16O11 70.50 -0.08 441.023125 C18H15O11Cl1 16.74 0.26 135 409.041217 C17H14O12 59.75 -0.08 443.002366 C17H13O12Cl1 12.40 0.20 136 419.061989 C19H16O11 58.20 0.01 453.023180 C19H15O11Cl1 14.21 0.37 137 431.062028 C20H16O11 43.65 0.10 465.023110 C20H15O11Cl1 11.45 0.21 138 433.041298 C19H14O12 51.31 0.11 467.002358 C19H13O12Cl1 12.92 0.17 139 435.056968 C19H16O12 75.47 0.16 469.018044 C19H15O12Cl1 17.73 0.25 140 445.041359 C20H14O12 37.26 0.25 479.002360 C20H13O12Cl1 10.37 0.17 141 447.057014 C20H16O12 60.51 0.26 481.018007 C20H15O12Cl1 15.88 0.17 142 449.036269 C19H14O13 49.56 0.24 482.997316 C19H13O13Cl1 11.27 0.26 143 459.057034 C21H16O12 44.97 0.29 493.017981 C21H15O12Cl1 11.87 0.11 144 461.036277 C20H14O13 43.42 0.25 494.997256 C20H13O13Cl1 11.01 0.13 145 593.033816 C24H19O16P1 12.00 0.04 626.994223 C24H18O16P1Cl1 5.30 -0.95 146 -a _-a _-a _-a _{240.990865 C} 10H7O5Cl1 1.86 -0.25

Chlorinated SRNOM in the presence of Br

-147 153.019376 C7H6O4 1.41 0.29 230.929809 C7H5O4Br1 1.40 -0.15 148 157.014293 C6H6O5 0.98 0.30 234.924603 C6H5O5Br1 0.91 -0.66 149 161.024401 C9H6O3 0.89 -0.10 238.934889 C9H5O3Br1 0.60 -0.17 150 324.836321 C8H4O4 4.28 -0.18 240.914144 C8H3O4Br1 1.96 -0.21 151 165.019322 C8H6O4 1.68 -0.06 242.929811 C8H5O4Br1 1.56 -0.14 152 169.014249 C7H6O5 1.48 0.01 246.924733 C7H5O5Br1 0.66 -0.11 153 177.019350 C9H6O4 2.07 0.10 254.929889 C9H5O4Br1 1.85 0.17 154 181.014291 C8H6O5 2.16 0.25 258.924766 C8H5O5Br1 4.73 0.03 155 185.009220 C7H6O6 1.09 0.32 262.919632 C7H5O6Br1 0.52 -0.16 156 190.998633 C9H4O5 1.32 0.19 268.909072 C9H3O5Br1 0.90 -0.14

157 197.009193 C8H6O6 2.27 0.16 274.919633 C8H5O6Br1 1.47 -0.15 158 197.045586 C9H10O5 3.07 0.20 274.955940 C9H9O5Br1 0.77 -0.43 159 199.024840 C8H8O6 1.98 0.15 276.935476 C8H7O6Br1 0.94 0.55 160 203.035000 C11H8O4 2.90 0.09 280.945552 C11H7O4Br1 1.22 0.20 161 205.014253 C10H6O5 4.10 0.03 282.924766 C10H5O5Br1 2.68 0.02 162 205.050632 C11H10O4 3.48 0.00 282.961150 C11H9O4Br1 1.16 0.02 163 368.826118 C9H4O6 2.54 -0.07 284.904000 C9H3O6Br1 3.95 -0.08 164 209.009167 C9H6O6 4.68 0.03 286.919676 C9H5O6Br1 5.46 0.01 165 211.024840 C9H8O6 4.23 0.14 288.935302 C9H7O6Br1 1.89 -0.08 166 217.014249 C11H6O5 3.46 0.01 294.924882 C11H5O5Br1 1.14 0.42 167 217.050635 C12H10O4 3.76 0.01 294.961297 C12H9O4Br1 0.86 0.52 168 219.029901 C11H8O5 6.36 0.02 296.940400 C11H7O5Br1 2.28 -0.03 169 382.841746 C10H6O6 2.36 -0.01 298.919665 C10H5O6Br1 4.58 -0.03 170 221.045550 C11H10O5 6.39 0.02 298.956167 C11H9O5Br1 2.08 0.36 171 265.035392 C12H10O7 16.13 0.06 298.996358 C12H9O7Cl1 1.75 -0.15 172 384.820967 C9H4O7 1.87 0.11 300.898855 C9H3O7Br1 0.82 -0.28 173 223.024814 C10H8O6 7.55 0.01 300.935329 C10H7O6Br1 5.85 0.02 174 223.061207 C11H12O5 5.81 0.05 300.971597 C11H11O5Br1 0.82 -0.37 175 225.004077 C9H6O7 6.05 0.01 302.914607 C9H5O7Br1 4.01 0.06 176 225.040473 C10H10O6 6.50 0.05 302.950943 C10H9O6Br1 2.22 -0.10 177 227.019685 C9H8O7 3.57 -0.18 304.930130 C9H7O7Br1 0.75 -0.36 178 227.056105 C10H12O6 6.94 -0.03 304.966755 C10H11O6Br1 0.93 0.43 179 231.029887 C12H8O5 5.40 -0.04 308.940386 C12H7O5Br1 1.56 -0.07 180 233.009160 C11H6O6 6.21 0.00 310.919675 C11H5O6Br1 2.09 0.00 181 233.045539 C12H10O5 7.48 -0.03 310.956122 C12H9O5Br1 1.92 0.20 182 234.988400 C10H4O7 3.46 -0.11 312.898885 C10H3O7Br1 1.33 -0.17 183 396.857427 C11H8O6 1.67 -0.09 312.935290 C11H7O6Br1 3.82 -0.11 184 398.836633 C10H6O7 2.28 0.06 314.914605 C10H5O7Br1 4.49 0.05 185 237.040450 C11H10O6 9.10 -0.05 314.950906 C11H9O6Br1 3.14 -0.21 186 239.019715 C10H8O7 8.07 -0.04 316.930250 C10H7O7Br1 4.22 0.04 187 239.056094 C11H12O6 9.80 -0.07 316.966681 C11H11O6Br1 1.43 0.18 188 240.998988 C9H6O8 2.92 -0.01 318.909447 C9H5O8Br1 1.02 -0.18 189 241.035362 C10H10O7 8.16 -0.06 318.945924 C10H9O7Br1 1.74 0.11

190 165.019322 C8H6O4 1.68 -0.06 320.840259 C8H4O4Br2 4.52 -0.31 191 245.009151 C12H6O6 4.06 -0.04 322.919776 C12H5O6Br1 0.96 0.32 192 245.045547 C13H10O5 6.70 0.00 322.956198 C13H9O5Br1 1.34 0.43 193 247.024797 C12H8O6 9.91 -0.06 324.935268 C12H7O6Br1 2.42 -0.17 194 247.061185 C13H12O5 8.02 -0.05 324.971888 C13H11O5Br1 1.26 0.55 195 249.004053 C11H6O7 8.29 -0.09 326.914559 C11H5O7Br1 3.08 -0.09 196 249.040447 C12H10O6 12.17 -0.06 326.951016 C12H9O6Br1 3.55 0.13 197 251.019728 C11H8O7 14.26 0.01 328.930222 C11H7O7Br1 6.97 -0.05 198 251.056115 C12H12O6 11.56 0.02 328.966690 C12H11O6Br1 1.91 0.20 199 252.998988 C10H6O8 8.40 -0.01 330.909519 C10H5O8Br1 4.73 0.05 200 253.035370 C11H10O7 11.76 -0.02 330.945882 C11H9O7Br1 4.13 -0.02 201 255.014636 C10H8O8 5.56 -0.02 332.925135 C10H7O8Br1 2.28 -0.05 202 255.051021 C11H12O7 14.61 -0.02 332.961560 C11H11O7Br1 1.74 0.07 203 181.014291 C8H6O5 2.16 0.25 336.835201 C8H4O5Br2 5.75 -0.21 204 259.024806 C13H8O6 7.94 -0.02 336.935287 C13H7O6Br1 1.81 -0.11 205 261.004073 C12H6O7 6.26 -0.01 338.914431 C12H5O7Br1 1.46 -0.46 206 261.040470 C13H10O6 11.66 0.03 338.950994 C13H9O6Br1 2.66 0.06 207 424.852384 C12H8O7 2.50 -0.18 340.930241 C12H7O7Br1 4.29 0.01 208 263.056125 C13H12O6 12.80 0.05 340.966709 C13H11O6Br1 2.49 0.25 209 264.998994 C11H6O8 8.75 0.01 342.909484 C11H5O8Br1 4.22 -0.06 210 265.035392 C12H10O7 16.13 0.06 342.945896 C12H9O7Br1 5.63 0.02 211 267.014654 C11H8O8 15.28 0.05 344.925156 C11H7O8Br1 7.95 0.01 212 267.051046 C12H12O7 18.27 0.08 344.961576 C12H11O7Br1 3.39 0.11 213 269.030310 C11H10O8 12.66 0.07 346.940789 C11H9O8Br1 3.46 -0.04 214 271.045950 C11H12O8 16.95 0.04 348.956525 C11H11O8Br1 1.69 0.21 215 273.040464 C14H10O6 9.63 0.01 350.951043 C14H9O6Br1 1.78 0.20 216 436.852017 C13H8O7 1.99 0.66 352.930178 C13H7O7Br1 3.02 -0.17 217 275.056109 C14H12O6 12.21 -0.01 352.966620 C14H11O6Br1 2.21 -0.01 218 276.999019 C12H6O8 8.89 0.10 354.909511 C12H5O8Br1 2.45 0.02 219 438.867879 C13H10O7 2.67 0.18 354.945879 C13H9O7Br1 4.58 -0.03 220 279.014666 C12H8O8 16.59 0.09 356.925171 C12H7O8Br1 5.53 0.05 221 279.051040 C13H12O7 20.05 0.05 356.961598 C13H11O7Br1 4.57 0.17 222 280.993933 C11H6O9 6.66 0.10 358.904389 C11H5O9Br1 2.67 -0.08

223 281.030300 C12H10O8 20.70 0.03 358.940775 C12H9O8Br1 6.33 -0.08 224 281.066686 C13H14O7 27.04 0.04 358.977211 C13H13O7Br1 2.37 0.06 225 283.009562 C11H8O9 10.36 0.03 360.920148 C11H7O9Br1 2.60 0.22 226 283.045946 C12H12O8 26.45 0.02 360.956513 C12H11O8Br1 3.38 0.17 227 209.009167 C9H6O6 4.68 0.03 364.830214 C9H4O6Br2 2.68 0.08 228 287.019724 C14H8O7 9.28 -0.01 364.930328 C14H7O7Br1 1.66 0.25 229 289.035372 C14H10O7 16.64 -0.01 366.945882 C14H9O7Br1 2.89 -0.02 230 291.014641 C13H8O8 15.35 0.00 368.925126 C13H7O8Br1 3.82 -0.07 231 291.051012 C14H12O7 20.86 -0.05 368.961608 C14H11O7Br1 3.49 0.19 232 293.030289 C13H10O8 24.00 0.00 370.940868 C13H9O8Br1 5.52 0.18 233 293.066672 C14H14O7 24.98 -0.01 370.977282 C14H13O7Br1 2.79 0.25 234 295.009547 C12H8O9 20.41 -0.03 372.920076 C12H7O9Br1 4.78 0.02 235 295.045941 C13H12O8 28.83 0.00 372.956483 C13H11O8Br1 5.16 0.08 236 297.025212 C12H10O9 18.32 0.02 374.935865 C12H9O9Br1 4.33 0.39 237 299.040842 C12H12O9 26.65 -0.04 376.951444 C12H11O9Br1 3.03 0.20 238 223.024814 C10H8O6 7.55 0.01 378.845977 C10H6O6Br2 2.50 0.37 239 225.004077 C9H6O7 6.05 0.01 380.825262 C9H4O7Br2 1.97 0.42 240 303.051032 C15H12O7 18.07 0.02 380.961682 C15H11O7Br1 2.72 0.38 241 466.862975 C14H10O8 2.51 -0.22 382.940870 C14H9O8Br1 4.80 0.18 242 307.009548 C13H8O9 15.44 -0.02 384.920165 C13H7O9Br1 3.54 0.25 243 307.045948 C14H12O8 29.07 0.03 384.956518 C14H11O8Br1 6.16 0.17 244 309.025193 C13H10O9 27.41 -0.04 386.935806 C13H9O9Br1 6.59 0.23 245 309.061581 C14H14O8 37.04 -0.03 386.972235 C14H13O8Br1 4.10 0.34 246 311.004445 C12H8O10 12.89 -0.08 388.915121 C12H7O10Br1 2.80 0.36 247 311.040845 C13H12O9 34.34 -0.03 388.951528 C13H11O9Br1 5.19 0.41 248 237.040450 C11H10O6 9.10 -0.05 392.861814 C11H8O6Br2 1.77 0.83 249 315.014637 C15H8O8 9.11 -0.01 392.925212 C15H7O8Br1 1.87 0.15 250 239.019715 C10H8O7 8.07 -0.04 394.841147 C10H6O7Br2 2.41 1.00 251 317.030267 C15H10O8 16.76 -0.07 394.940980 C15H9O8Br1 3.54 0.45 252 480.878431 C15H12O8 2.11 0.19 396.956517 C15H11O8Br1 4.75 0.16 253 321.025181 C14H10O9 24.77 -0.07 398.935779 C14H9O9Br1 5.73 0.15 254 321.061588 C15H14O8 31.46 -0.01 398.972265 C15H13O8Br1 4.16 0.41 255 323.040838 C14H12O9 36.65 -0.05 400.951506 C14H11O9Br1 6.90 0.35

256 325.020108 C13H10O10 22.05 -0.04 402.930842 C13H9O10Br1 3.80 0.52 257 325.056491 C14H14O9 53.80 -0.04 402.967213 C14H13O9Br1 4.51 0.49 258 327.035765 C13H12O10 32.04 -0.01 404.946596 C13H11O10Br1 3.26 0.78 259 331.045916 C16H12O8 21.08 -0.07 408.956501 C16H11O8Br1 3.45 0.12 260 494.857781 C15H10O9 2.46 0.01 410.935795 C15H9O9Br1 4.86 0.19 261 333.061569 C16H14O8 28.86 -0.06 410.972288 C16H13O8Br1 3.94 0.45 262 335.040841 C15H12O9 36.72 -0.04 412.951414 C15H11O9Br1 7.79 0.11 263 337.020109 C14H10O10 28.50 -0.03 414.930756 C14H9O10Br1 5.68 0.30 264 337.056495 C15H14O9 49.57 -0.03 414.967031 C15H13O9Br1 6.68 0.03 265 339.035767 C14H12O10 42.33 -0.01 416.946477 C14H11O10Br1 6.87 0.47 266 341.051416 C14H14O10 63.87 -0.01 418.962197 C14H13O10Br1 4.76 0.63 267 265.035392 C12H10O7 16.13 0.06 420.856717 C12H8O7Br2 2.64 0.75 268 343.009519 C16H8O9 8.62 -0.10 420.919847 C16H7O9Br1 1.71 -0.52 269 345.025176 C16H10O9 17.62 -0.08 422.935673 C16H9O9Br1 3.64 -0.11 270 508.873270 C16H12O9 2.69 0.33 424.951359 C16H11O9Br1 6.23 -0.02 271 349.020112 C15H10O10 24.55 -0.02 426.930818 C15H9O10Br1 5.02 0.44 272 349.056486 C16H14O9 42.51 -0.05 426.967100 C16H13O9Br1 7.33 0.19 273 351.035758 C15H12O10 45.28 -0.03 428.946378 C15H11O10Br1 8.54 0.22 274 351.072149 C16H16O9 54.81 -0.02 428.982937 C16H15O9Br1 4.77 0.63 275 438.867879 C13H10O7 2.67 0.18 432.856668 C13H8O7Br2 2.10 0.62 276 398.999461 C18H8O11 5.74 0.19 432.960030 C18H7O11Cl1 7.70 -0.88 277 355.067059 C15H16O10 86.75 -0.03 432.977805 C15H15O10Br1 4.44 0.51 278 279.051040 C13H12O7 20.05 0.05 434.872341 C13H10O7Br2 2.82 0.67 279 359.004434 C16H8O10 8.49 -0.10 436.915017 C16H7O10Br1 2.38 0.08 280 359.040841 C17H12O9 24.31 -0.04 436.951120 C17H11O9Br1 4.06 -0.57 281 361.020108 C16H10O10 21.17 -0.03 438.930582 C16H9O10Br1 4.40 -0.11 282 361.056491 C17H14O9 34.54 -0.04 438.967038 C17H13O9Br1 5.19 0.05 283 363.035771 C16H12O10 39.15 0.00 440.946443 C16H11O10Br1 7.50 0.36 284 365.051415 C16H14O10 56.92 -0.01 442.962042 C16H13O10Br1 9.12 0.25 285 367.030682 C15H12O11 41.71 -0.01 444.941440 C15H11O11Br1 6.46 0.55 286 367.067064 C16H16O10 72.03 -0.01 444.977719 C16H15O10Br1 5.92 0.31 287 369.046339 C15H14O11 65.24 0.01 446.957193 C15H13O11Br1 5.94 0.77 288 375.035780 C17H12O10 30.81 0.03 452.946204 C17H11O10Br1 6.01 -0.17

289 377.015048 C16H10O11 20.41 0.04 454.925657 C16H9O11Br1 3.78 0.24 290 377.051432 C17H14O10 48.59 0.03 454.961986 C17H13O10Br1 7.65 0.12 291 379.030684 C16H12O11 43.76 0.00 456.941428 C16H11O11Br1 6.67 0.51 292 379.067085 C17H16O10 61.28 0.04 456.977596 C17H15O10Br1 6.69 0.03 293 381.046353 C16H14O11 67.45 0.05 458.957070 C16H13O11Br1 8.33 0.49 294 383.061993 C16H16O11 89.62 0.02 460.972836 C16H15O11Br1 5.65 0.74 295 307.045948 C14H12O8 29.07 0.03 462.867258 C14H10O8Br2 2.65 0.63 296 391.030726 C17H12O11 36.98 0.11 468.941246 C17H11O11Br1 6.20 0.11 297 393.046357 C17H14O11 58.00 0.06 470.956948 C17H13O11Br1 8.41 0.22 298 395.025635 C16H12O12 34.99 0.09 472.936281 C16H11O12Br1 4.35 0.36 299 395.062007 C17H16O11 73.21 0.06 472.972581 C17H15O11Br1 6.40 0.18 300 321.061588 C15H14O8 31.46 -0.01 476.882653 C15H12O8Br2 2.23 0.08 301 403.030730 C18H12O11 30.23 0.11 480.940971 C18H11O11Br1 5.04 -0.47 302 405.046374 C18H14O11 51.50 0.10 482.956805 C18H13O11Br1 7.35 -0.09 303 407.062023 C18H16O11 67.82 0.10 484.972433 C18H15O11Br1 7.61 -0.13 304 409.041287 C17H14O12 67.10 0.09 486.951842 C17H13O12Br1 7.54 0.17 305 335.040841 C15H12O9 36.72 -0.04 490.862171 C15H10O9Br2 2.60 0.59 306 417.046400 C19H14O11 43.71 0.16 494.956384 C19H13O11Br1 5.76 -0.93 307 419.025667 C18H12O12 36.45 0.16 496.936249 C18H11O12Br1 4.70 0.28 308 419.062042 C19H16O11 59.22 0.14 496.972195 C19H15O11Br1 6.80 -0.61 309 421.041296 C18H14O12 64.66 0.11 498.951917 C18H13O12Br1 8.08 0.31 310 421.077656 C19H18O11 65.95 0.05 498.987818 C19H17O11Br1 5.54 -0.66 311 423.056957 C18H16O12 86.58 0.14 500.967586 C18H15O12Br1 8.14 0.35 312 349.056486 C16H14O90 42.51 -0.05 504.877534 C16H12O9Br2 2.84 0.01 313 433.041316 C19H14O12 53.10 0.16 510.951713 C19H13O12Br1 6.88 -0.09 314 435.056961 C19H16O12 73.14 0.14 512.967329 C19H15O12Br1 8.08 -0.16 315 437.036234 C18H14O13 57.77 0.16 514.946962 C18H13O13Br1 6.05 0.56 316 437.072589 C19H18O12 81.15 0.09 514.982973 C19H17O12Br1 6.07 -0.17 317 445.041301 C20H14O12 39.36 0.12 522.951352 C20H13O12Br1 4.91 -0.78 318 447.056929 C20H16O12 58.93 0.07 524.967232 C20H15O12Br1 6.56 -0.34 319 449.036214 C19H14O13 53.37 0.11 526.946906 C19H13O13Br1 6.39 0.44 320 449.072600 C20H18O12 68.65 0.11 526.982820 C20H17O12Br1 6.19 -0.46 321 461.036212 C20H14O13 41.12 0.11 538.946750 C20H13O13Br1 5.39 0.14

322 463.051868 C20H16O13 62.22 0.12 540.962375 C20H15O13Br1 7.89 0.09 323 475.051849 C21H16O13 47.63 0.08 552.962125 C21H15O13Br1 6.08 -0.36 324 477.067495 C21H18O13 59.72 0.07 554.977846 C21H17O13Br1 6.18 -0.23 325 489.067486 C22H18O13 47.70 0.05 566.977505 C22H17O13Br1 4.71 -0.83 326 491.046742 C21H16O14 52.87 0.03 568.957526 C21H15O14Br1 5.91 0.50 327 503.046758 C22H16O14 43.71 0.06 580.957399 C22H15O14Br1 4.63 0.27 328 517.062377 C23H18O14 42.75 0.00 594.972920 C23H17O14Br1 4.42 0.05 329 531.078056 C24H20O14 38.32 0.05 608.988310 C24H19O14Br1 3.51 -0.38 330 533.057308 C23H18O15 47.34 0.03 610.967743 C23H17O15Br1 4.47 -0.10 331 535.072927 C23H20O15 54.66 -0.03 612.983463 C23H19O15Br1 4.16 0.01 332 539.067858 C22H20O16 50.26 0.00 616.978804 C22H19O16Br1 3.51 0.70 333 540.980986 C23H11O14P1 5.82 -0.70 618.891778 C23H10O14P1Br1 2.49 -0.16 334 557.057262 C25H18O15 26.84 -0.05 634.968220 C25H17O15Br1 3.11 0.65 335 561.088582 C25H22O15 36.58 -0.02 638.998672 C25H21O15Br1 2.83 -0.68 336 565.083559 C24H22O16 45.39 0.09 642.994153 C24H21O16Br1 3.44 0.21 337 566.960390 C24H9O15P1 4.80 -0.42 644.871537 C24H8O15P1Br1 2.09 0.61 338 567.062826 C23H20O17 36.70 0.10 644.973678 C23H19O17Br1 3.14 0.61 339 575.067788 C25H20O16 34.90 -0.12 652.978877 C25H19O16Br1 3.98 0.78 340 577.083551 C25H22O16 39.19 0.08 654.994200 C25H21O16Br1 3.58 0.28 341 579.062761 C24H20O17 36.19 -0.02 656.973398 C24H19O17Br1 3.42 0.17 342 580.976349 C25H11O15P1 4.65 0.12 658.886383 C25H10O15P1Br1 2.53 -0.62 343 581.078420 C24H22O17 38.44 0.00 658.988716 C24H21O17Br1 2.78 -0.33 344 582.992150 C25H13O15P1 3.83 0.38 660.901976 C25H12O15P1Br1 2.55 -0.70 345 584.971506 C24H11O16P1 5.66 0.53 662.881862 C24H10O16P1Br1 2.97 0.24 346 586.987275 C24H13O16P1 5.09 0.73 664.897024 C24H12O16P1Br1 2.46 -0.50 347 598.987027 C25H13O16P1 4.67 0.31 676.897576 C25H12O16P1Br1 2.56 0.32 348 605.078382 C26H22O17 30.71 -0.07 682.989498 C26H21O17Br1 3.34 0.83 349 607.093968 C26H24O17 28.46 -0.17 685.003940 C26H23O17Br1 2.72 -0.94 350 609.073260 C25H22O18 27.07 -0.13 686.983484 C25H21O18Br1 2.50 -0.53 351 619.094020 C27H24O17 24.27 -0.08 697.005133 C27H23O17Br1 2.45 0.79 352 621.073289 C26H22O18 24.54 -0.08 698.983982 C26H21O18Br1 2.96 0.19 353 628.997732 C26H15O17P1 3.78 0.51 706.907774 C26H14O17P1Br1 2.25 -0.21 354 637.068154 C26H22O19 17.53 -0.15 714.979081 C26H21O19Br1 1.90 0.44

355 638.982123 C27H13O17P1 3.60 0.57 716.892704 C27H12O17P1Br1 2.40 0.60 356 647.088948 C28H24O18 21.67 -0.06 724.999973 C28H23O18Br1 2.26 0.65 357 663.083905 C28H24O19 22.20 0.01 740.994936 C28H23O19Br1 2.24 0.71 358 668.992716 C28H15O18P1 3.56 0.59 746.903004 C28H14O18Br1P1 1.57 0.23 359 676.980377 C28H10O19N2 2.82 -0.18 754.891232 C28H9O19N2Br1 1.86 0.29 360 161.024401 C9H6O3 0.89 -0.10 256.945516 C9H7O4Br1 1.99 0.08 361 177.019350 C9H6O4 2.07 0.10 272.940376 C9H7O5Br1 2.52 -0.12 362 247.024777 C12H8O6 6.60 -0.14 298.996358 C12H9O7Cl1 1.75 -0.15 363 -a _-a _-a _-a _{170.845078 C} 1H2Br2 3.33 0.17 364 -a _-a _-a _-a _{214.834885 C} 2H2O2Br2 5.64 0.03 365 -a _-a _-a _-a _{214.934884 C} 7H5O3Br1 1.69 -0.21 366 -a _-a _-a _-a _{222.880281 C} 4H2O4P1Br1 0.72 0.67 367 -a _-a _-a _-a _{228.950516 C} 8H7O3Br1 0.78 0.30 368 -a _-a _-a _-a _{240.950612 C} 9H7O3Br1 0.66 0.13 369 -a _-a _-a _-a _{266.929778 C} 10H5O4Br1 1.00 -0.25 370 -a _-a _-a _-a _{268.945487 C} 10H7O4Br1 1.58 -0.03 371 -a _-a _-a _-a _{270.924801 C} 9H5O5Br1 3.39 0.15 372 -a _-a _-a _-a _{276.850602 C} 7H4O2Br2 0.87 0.30 373 -a _-a _-a _-a _{284.940441 C} 10H7O5Br1 3.30 0.11 374 -a _-a _-a _-a _{286.956133 C} 10H9O5Br1 1.60 0.26 375 -a _-a _-a _-a _{292.845454 C} 7H4O3Br2 8.25 0.04 376 -a _-a _-a _-a _{306.860864 C} 8H6O3Br2 1.45 -0.74 377 -a _-a _-a _-a _{334.855920 C} 9H6O4Br2 1.52 -0.26 378 -a _-a _-a _-a _{350.851125 C} 9H6O5Br2 1.51 0.58 379 -a _-a _-a _-a _{362.851006 C} 10H6O5Br2 1.81 0.23 380 -a _-a _-a _-a _{364.866717 C} 10H8O5Br2 1.66 0.40 381 -a _-a _-a _-a _{370.755915 C} 7H3O3Br3 1.51 -0.11 382 -a _-a _-a _-a _{534.870555 C} 19H6O12P1Br1 3.77 -0.36 383 -a _-a _-a _-a _{602.860346 C} 22H6O14P1Br1 2.09 -0.38 384 -a _-a _-a _-a _{604.876103 C} 22H8O14 P1Br1 2.80 -0.21 385 -a _-a _-a _-a _{632.870898 C} 23H8O15P1Br1 2.35 -0.38 Odaiba Seawater 386 269.139447 C14H22O5 2.55 0.00 303.100364 C14H21O5Cl1 0.50 -0.36

387 285.134360 C14H22O6 3.93 0.00 319.095380 C14H21O6Cl1 0.78 -0.03 388 297.134345 C15H22O6 7.18 -0.05 331.095398 C15H21O6Cl1 0.83 0.03 389 299.150018 C15H24O6 4.28 0.02 333.111118 C15H23O6Cl1 0.90 0.24 390 337.202033 C19H30O5 2.18 -0.04 371.163152 C19H29O5Cl1 0.92 0.21 391 339.181300 C18H28O6 4.26 -0.03 373.142434 C18H27O6Cl1 1.31 0.26 392 353.160565 C18H26O7 8.85 -0.03 387.121718 C18H25O7Cl1 0.97 0.30 393 353.196970 C19H30O6 2.96 0.03 387.158038 C19H29O6Cl1 1.28 0.13 394 355.176205 C18H28O7 4.95 -0.06 389.137328 C18H27O7Cl1 1.37 0.19 395 355.212569 C19H32O6 1.48 -0.12 389.173633 C19H31O6Cl1 0.90 -0.01 396 293.124157 C12H22O8 0.64 -0.11 395.007286 C12H19O8Cl3 8.47 0.03 397 367.212591 C20H32O6 3.95 -0.05 401.173724 C20H31O6Cl1 1.41 0.21 398 369.191868 C19H30O7 4.36 -0.02 403.153050 C19H29O7Cl1 1.55 0.36 399 381.191889 C20H30O7 7.30 0.03 415.152995 C20H29O7Cl1 1.63 0.22 400 295.139710 C12H24O8 0.45 -0.44 430.983997 C12H20O8Cl4 24.19 0.11 401 411.238885 C22H36O7 1.42 0.14 445.199610 C22H35O7Cl1 2.09 -0.55 402 543.236449 C26H41P1O10 0.60 -0.01 577.197076 C26H40O10P1Cl1 0.85 -0.71 403 593.228368 C27H46O8S3 0.54 0.28 695.110590 C27H43O8S3Cl3 1.16 -1.00 a _{Precursors not detected;}

Table S7. Putative non-halogenated byproducts formed during the chlorination of SRNOM.

m/z

Formula O/C H/C

RA

SRNOM ClO ClO+Br SRNOM ClO ClO+Br

161.024381 161.024381 161.024401 C9H6O3 0.33 0.67 0.00 0.67 0.89 165.01929 165.019324 165.019322 C8H6O4 0.50 0.75 0.46 1.26 1.68 165.055739 165.055739 165.055718 C9H10O3 0.33 1.11 0.00 0.92 1.45 167.035021 167.035021 167.035031 C8H8O4 0.50 1.00 0.00 1.39 1.75 181.014309 181.014309 181.014291 C8H6O5 0.63 0.75 0.00 1.65 2.16 181.086937 181.086937 181.08707 C10H14O3 0.30 1.40 0.00 0.60 0.97 183.029895 183.029895 183.02993 C8H8O5 0.63 1.00 0.00 1.33 1.95 183.066402 183.066284 183.066345 C9H12O4 0.44 1.33 0.60 1.24 1.38 185.009202 185.009202 185.00922 C7H6O6 0.86 0.86 0.00 0.99 1.09 185.045574 185.045574 185.045572 C8H10O5 0.63 1.25 0.00 1.38 1.81 197.00919 197.0092 197.009193 C8H6O6 0.75 0.75 0.74 1.94 2.27 197.045556 197.045556 197.045586 C9H10O5 0.56 1.11 0.00 2.32 3.07 203.071431 203.071431 203.071372 C12H12O3 0.25 1.00 0.00 1.47 1.72 206.993545 206.993545 206.993517 C9H4O6 0.67 0.44 0.00 1.33 1.90 209.009282 209.009215 209.009167 C9H6O6 0.67 0.67 0.68 2.81 4.68 211.024836 211.024836 211.02484 C9H8O6 0.67 0.89 0.00 3.02 4.23 211.061237 211.061251 211.061219 C10H12O5 0.50 1.20 2.14 3.69 4.32 213.040501 213.040501 213.040479 C9H10O6 0.67 1.11 0.00 3.69 4.07 213.055789 213.055789 213.055706 C13H10O3 0.23 0.77 0.00 0.60 0.93 215.035018 215.034976 215.03499 C12H8O4 0.33 0.67 0.59 1.25 2.28 217.014282 217.014282 217.014249 C11H6O5 0.45 0.55 0.00 2.11 3.46 217.050639 217.050639 217.050635 C12H10O4 0.33 0.83 0.00 2.71 3.76 221.009165 221.00922 221.009166 C10H6O6 0.60 0.60 1.73 3.97 6.36 223.02484 223.024824 223.024814 C10H8O6 0.60 0.80 2.78 5.44 7.55 223.061216 223.061216 223.061207 C11H12O5 0.45 1.09 0.00 4.88 5.81 225.00418 225.004015 225.004077 C9H6O7 0.78 0.67 0.84 2.27 6.05 225.040473 225.040438 225.040473 C10H10O6 0.60 1.00 3.29 5.49 6.50 227.019745 227.019745 227.019685 C9H8O7 0.78 0.89 0.00 2.76 3.57 227.056101 227.056101 227.056105 C10H12O6 0.60 1.20 0.00 6.06 6.94

229.071752 229.071752 229.071769 C10H14O6 0.60 1.40 0.00 5.15 5.33 230.993442 230.993442 230.993589 C11H4O6 0.55 0.36 0.00 0.88 1.85 231.029866 231.029866 231.029887 C12H8O5 0.42 0.67 0.00 3.49 5.40 233.009146 233.009141 233.00916 C11H6O6 0.55 0.55 1.44 3.28 6.21 233.045525 233.045518 233.045539 C12H10O5 0.42 0.83 3.55 5.35 7.48 234.988445 234.988419 234.9884 C10H4O7 0.70 0.40 0.59 2.09 3.46 235.02479 235.02479 235.024797 C11H8O6 0.55 0.73 3.58 7.48 9.88 237.004124 237.004064 237.004057 C10H6O7 0.70 0.60 1.01 3.39 7.63 237.040439 237.04044 237.04045 C11H10O6 0.55 0.91 4.62 7.76 9.10 239.019682 239.019687 239.019715 C10H8O7 0.70 0.80 2.36 5.68 8.07 240.99896 240.99896 240.998988 C9H6O8 0.89 0.67 0.00 1.40 2.92 241.035341 241.035341 241.035362 C10H10O7 0.70 1.00 0.00 6.41 8.16 241.086892 241.086892 241.087044 C15H14O3 0.20 0.93 0.00 0.93 1.09 243.01465 243.014589 243.014622 C9H8O8 0.89 0.89 0.63 1.98 2.61 243.050983 243.050983 243.051002 C10H12O7 0.70 1.20 0.00 7.07 9.55 245.009184 245.009114 245.009151 C12H6O6 0.50 0.50 1.28 2.24 4.06 245.066653 245.066653 245.066662 C10H14O7 0.70 1.40 0.00 4.84 5.08 245.081931 245.081931 245.081888 C14H14O4 0.29 1.00 0.00 3.12 3.92 245.103015 245.103015 245.102991 C11H18O6 0.55 1.64 0.00 1.74 1.89 246.988205 246.988451 246.988439 C11H4O7 0.64 0.36 0.51 1.42 2.34 247.024769 247.024777 247.024797 C12H8O6 0.50 0.67 3.28 6.60 9.91 249.003961 249.004043 249.004053 C11H6O7 0.64 0.55 1.45 4.60 8.29 249.040425 249.04042 249.040447 C12H10O6 0.50 0.83 5.88 9.56 12.17 250.983437 250.983437 250.983328 C10H4O8 0.80 0.40 0.00 1.48 6.54 251.019671 251.019681 251.019728 C11H8O7 0.64 0.73 3.21 9.39 14.26 252.998773 252.998937 252.998988 C10H6O8 0.80 0.60 0.64 2.89 8.40 253.035355 253.035342 253.03537 C11H10O7 0.64 0.91 5.02 8.97 11.76 255.014586 255.014627 255.014636 C10H8O8 0.80 0.80 1.22 3.24 5.56 255.029868 255.029868 255.029934 C14H8O5 0.36 0.57 0.00 1.95 2.81 255.051002 255.050993 255.051021 C11H12O7 0.64 1.09 7.39 11.24 14.61 255.066242 255.066242 255.066288 C15H12O4 0.27 0.80 0.00 1.83 2.68 255.102444 255.102444 255.102628 C16H16O3 0.19 1.00 0.00 0.87 0.98 257.008914 257.009092 257.009162 C13H6O6 0.46 0.46 0.67 1.63 2.70