Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
1 1
Expl
orin
g th
e ca
use
of
sour
ce w
ater
con
tam
inat
ion
usin
g LC
/MS/
MS
Nov
. 26,
201
5, U
T
Mar
i ASA
MI,
Dr.
Eng.
Chi
ef S
enio
r Res
earc
her
Wat
er M
anag
emen
t Fie
ldD
epar
tmen
t of E
nviro
nmen
tal H
ealth
N
atio
nal I
nstit
ute
of P
ublic
Hea
lth／
Prof
esso
rR
ECW
ET, t
he U
nive
rsity
of T
okyo
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Res
earc
h to
pics
Ris
k m
anag
emen
t and
che
mic
al a
naly
sis
inw
ater
sou
rce
and
drin
king
wat
er u
sing
LC
/MS
/MS 2
Col
labo
ratio
n of
re
sear
ch a
nd
prac
tice
Res
earc
h pr
omot
ion
Ref
lect
ion
to ri
sk
man
agem
ent
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Dev
elop
men
t of a
naly
tical
m
etho
d fo
r LC
(IC)/M
S/M
S
3
・W
eha
vede
velo
ped
anal
ytic
alm
etho
ds,c
ondu
ct fi
rst
natio
nals
urve
yan
d di
d ris
k as
sess
men
t res
pect
ivel
y on
B
rom
ate(
IC, I
C/M
S/M
S a
nd L
C/M
S/M
S),
perc
hlor
ate(
IC/M
S/M
S a
nd L
C/M
S/M
S),
chlo
rate
(IC),
and
ND
MA
(SP
E-L
C/M
S/M
S)
•C
olle
ct w
ater
qua
lity
acci
dent
s re
late
d to
hea
lth is
sues
•C
ontri
butio
n to
gui
delin
es fo
r w
ater
saf
ety
plan
s
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
4
O3
Br－
HO
Br
H+ +
OBr
－
BrO
2･Br･
O3
O3
BrO
3－
BrO･
BrO
2－
O3
OH･
OH･
Ozo
ne M
echa
nism
OH･
Radi
cal M
echa
nism
disp
ropo
rtio
natio
n
Con
trol o
f tox
ic d
isin
fect
ion
by-p
rodu
cts
(DB
Ps)
Nat
iona
l sur
vey
Pro
duct
ion
of c
arci
noge
nic
com
poun
d, b
rom
ate
in o
zona
tion
as a
dvan
ced
wat
er tr
eatm
ent
Dev
elop
men
t of a
naly
tical
m
etho
d of
bro
mat
e
Con
trol m
etho
d
Hig
h co
ncen
tratio
n of
bro
mat
e fo
rmat
ion
in c
ities
of h
igh
brom
ide,
trea
tmen
t at h
igh
pH,
high
dos
e of
ozo
ne, a
nd h
igh
tem
pera
ture
Bro
mat
e w
as in
trodu
ced
into
W
Q s
tand
ard,
con
trolle
d by
pH
an
d oz
one
dose
.
Maj
or in
form
atio
n in
trodu
ced
in
adva
nced
wat
er tr
eatm
ent
syst
ems
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Iden
tific
atio
n of
toxi
c N
DM
A(1
/2)
Look
ed fo
r in
flow
of
WW
TPs
inup
stre
amar
ea
5
Frac
tiona
tion
and
ozon
atio
n
NN
OH
3C
H3C
ND
MA
10
-5ca
ncer
pot
ency
(IRIS
): 7
ng/L
W
HO
GD
WQ
: 100
ng/
L
Japa
nese
ref.:
100
ng/
L
Dev
elop
men
t of a
naly
tical
m
etho
d fo
r ND
MA
Nat
iona
l sur
vey
Yodo
riv
er
Inflo
w
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Iden
tific
atio
n of
toxi
c N
DM
A (2
/2)
6
Nat
iona
l sur
vey
Can
dida
tes
for “
Trou
blin
g su
bsta
nces
for w
ater
trea
tmen
t”
Tota
l Ion
Chr
omat
ogra
m (f
ract
ion
no.1
3 )
Tota
l Ion
Chr
omat
ogra
m (f
ract
ion
no.1
5 )
Nat
iona
l sur
vey
of H
DM
S a
nd
TMD
S c
once
ntra
tions
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
ND
MA
beh
avio
r in
ozo
natio
nan
d A
C p
roce
ss
0510152025
原水
沈殿
水オ
ゾン
処理
水B
AC
処理
水浄
水
NDMA濃度 (ng/L)
D浄
水場
E浄水
場F浄
水場
G浄
水場
H浄
水場
I浄水
場
WTP
s in
Yod
oriv
er
7
Yodo
river
bas
in w
asa
spec
ial a
rea
whi
ch h
ave
ND
MA
ozon
atio
n pr
ecur
sor(
s)in
the
wor
ld.
Asam
i et a
l. (2
009)
Sci
. Tot
al E
nviro
n. 3
540.
Raw
S
edim
enta
tion
Ozo
natio
n B
AC
F
inis
hed
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
NDM
Aan
d its
form
atio
n po
tent
ials
(ND
MAF
P)
at in
flow
pip
es o
f the
AW
aste
wat
er
trea
tmen
t pla
nt
8In
flow
pip
esAn
othe
r W
WTP
7500
0O
rigin
alN
DM
AFP
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
9
6.2
2800
ND
MA（
ng/L
）
ND
MA
FP（
ng/L
）
5.0 56
8.1
5400
23
2600
0
47 40Fa
ctor
y X
1875
000
Inflo
w
pipe
6
ND
MA
and
ND
MA
FPat
inflo
w p
ipes
in u
pstre
am
A re
sult
in a
noth
er d
ate
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
0
300
600
900
1200
1500
1800
0.5-
4.5
4.5-
8.5
8.5-
12.5
12.5
-16.
516
.5-2
0.5
20.5
-24.
524
.5-2
8.5
28.5
-32.
532
.5-3
6.5
36.5
-40.
5
フラ
クシ
ョン
（分
）
NDMA濃度（ng/L）
Ozo
natio
n N
DM
AFP
Ano
ther
com
pone
nt in
the
fract
ion
no.4
-8 in
the
disc
harg
e fo
rm th
e fa
ctor
y X
.
10
NH
H NN
CH
3
CH
3
O
C H2
HN
H NN C
H3
H3C
O
TMD
S
N HN H
NH
3C
CH
3O
H NH N
NO
CH
3
CH
3
HD
MS
Th
ere
shou
ld b
e a
hydr
ophi
lic c
ompo
und(
s) in
the
fract
ion
no.4
-8 in
the
X fa
ctor
y.
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
0
300
600
900
1200
1500
1800
0.5-
1.5
1.5-
2.5
2.5-
3.5
3.5-
4.5
4.5-
5.5
5.5-
6.5
6.5-
7.5
7.5-
8.5
8.5-
9.5
9.5-
10.5
10.5
-11.
511
.5-1
2.5
フラ
クシ
ョン
（分
）
NDMA濃度（ng/L）
11
The
fract
ion
no.5
sh
owed
hig
h N
DM
AFP
The
fract
ion
no.5
sho
wed
hig
h “O
zona
tion
ND
MA
FP”
in th
e di
scha
rge
from
the
fact
ory
A.
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
03691215
02
46
810
強度（×108）
保持
時間
（分
）
12
Prod
uct i
on s
can
spec
trum
m/z
147
NH 3
C
H 3C
H NCO
H NN
CH3
CH3
TMCH
UPLC
M
S of
Tot
al Io
n Ch
rom
atog
ram
fract
ion
no.5
020406080100
4060
8010
012
014
016
0
相対強度（%）
m/z
Re
tent
ion
time
and
spec
trum
of
UPLC
M
S/M
S
Accu
rate
mas
s an
alys
isus
ing
TOF-
MS
Peal
in t
he fr
actio
n：14
7.12
46Sy
nthe
size
d TM
CH：
147.
1243
1 H
-NM
R/
13C-
NMR
Iden
tific
atio
n of
TM
CH（
1,1,
5,5-
tetr
amet
hyl c
arbo
nohy
draz
id)
rete
ntio
n tim
e (m
in)
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
13
NH
2NC
H 3
CH 3
NS
CH 3
CH 3
O
O
NH2
H 3C
NS
NOO
CH 3CH
3
SC
Cl
Cl
F
NN
OH 3
C
H 3C
UD
MH
（80
%）
ND
MA
form
atio
n at
mol
%
ND
MA
DM
S（
52%
）
TMD
S（
27%
）
Toly
lflua
nid（
9%）
HD
MS（
10%
）
TM
CH
-a s
peci
al c
hem
ical
in p
aper
and
prin
ting
indu
stry
To
lylfl
uani
d, a
pes
ticid
e pr
ohib
ited
in E
U w
ater
sou
rce,
bec
ause
DM
S, i
ts
degr
adat
ion
by-p
rodu
ct w
as fo
und
in h
igh
prod
uctio
n
HD
MS
, TM
DS
-clo
se to
TM
CH
, pre
viou
sly
foun
d by
our
team
NH 3
C
H 3C
H NCO
H NN
CH3
CH3
TMC
H（
150%
）
ND
MA
form
atio
n fro
m T
MC
H a
nd o
ther
re
porte
d su
bsta
nces
Ant
i-yel
low
ing
agen
t
Pes
ticid
e/de
grad
ates
Pre
vent
ion
of
deco
lorin
g
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Acco
unta
bilit
y of
the
chem
ical
s to
ND
MAF
Pin
the
A W
WTP
14
020406080100
1次2次
放流
水1次
2次放
流水
2014
年1月
2014
年2月
全NDMA前駆物質に占める割合（%）
TMDS TM
CH
HDM
S Fina
llyde
term
ined
Accountability of the compounds to NDMAFPin the A WWTP
1st
2nd
Fina
l
Jan
2014
1st
2nd
Fina
l
Feb
2014
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
MS
anal
ysis
and
iden
tific
atio
n of
NDM
AFP 15
02
46
810
時間
（分
）
Concentr
atio
n
HP
LCfr
actionat
ion
UP
LC–M
S/M
S
Find
ing
the
sour
ce o
f ND
MA
UP
LC–T
OF/
MS
NM
R
Syn
thes
is
NH
3C
H3C
H NCO
H NN
CH
3
CH
3
MS a
nal
ysis
2800
5654
002600
040X ND
MA
in s
ewag
e（n
g/L ）
ND
MA
0
500
1000
1500
2000
0.5-
1.5
1.5-
2.5
2.5-
3.5
3.5-
4.5
4.5-
5.5
5.5-
6.5
6.5-
7.5
7.5-
8.5
8.5-
9.5
9.5-
10.5
10.5
-11.
511.
5-12
.5
フラ
クシ
ョン
（分
）
Frac
tiona
ted
ND
MA （
ng/L
）
TIC
02
46
810
時間
（分
）
プロ
ダク
トイ
オン
スキ
ャン
4060
8010
012
014
016
0m
/z
プロ
ダク
トイ
オン
スペ
クト
ル
Iden
tific
atio
n of
hig
h co
ntrib
utor
of
ND
MA
form
atio
n
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
16
05
10
15
20 To
neTo
neTo
ne Mus
ashi
Tone
Kans
ai Kans
ai Kans
ai Other
s Other
s Other
s Other
s
Raw
Fin
ished
Perchlorateg
/l
Per
chlo
rate
is a
hyd
roph
ilic
cont
amin
ant u
sed
for r
ocke
t fue
l, ai
r ba
gs a
nd fi
rew
orks
.
Foun
d at
rath
er h
ighe
r con
cent
ratio
n in
Tok
yo m
etro
polit
an a
rea
Look
ed fo
r the
sou
rces
Req
uest
ed th
e re
duct
ion
of
disc
harg
e
Ana
lysi
s an
d co
ntro
l of
perc
hlor
ate
(ClO
4- )
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Exp
osur
e an
alys
is o
f hyd
roph
ilic
chem
ical
s in
wat
er a
nd fo
ods
17
Dat
a of
chl
orat
e an
d pe
rchl
orat
e in
fo
od w
as n
ot a
vaila
ble
due
to
diffi
culti
es in
ana
lysi
s
Dev
elop
ed a
naly
tical
met
hod
usin
g is
otop
e an
d LC
/MS
/MS
Exp
osur
e (in
take
) sur
vey
for
chlo
rate
and
per
chlo
rate
for e
ach
food
grou
ps u
sing
mar
ket –
bask
et
met
hod
Hig
h co
ntrib
utio
n of
wat
er s
uppl
y
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Tota
l int
ake
of c
hlor
ate
Tota
l int
ake
of p
erch
lora
te
Inta
ke
from
w
ater
isim
porta
nt
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Acc
iden
tal d
isch
arge
of a
form
alde
hyde
pr
ecur
sor i
nto
the
Tone
rive
r in
2012
Form
alde
hyde
was
det
ecte
d ab
ove
the
WQ
sta
ndar
d, in
the
upst
ream
of
Ton
e riv
er.
The
chem
ical
“Hex
amin
e” w
as d
isch
arge
d in
to th
e To
ne
river
, whi
ch w
as ju
st a
60
tons
. It
caus
ed w
ater
sus
pens
ion
for 8
50
thou
sand
peo
ple.
Was
te
trea
tmen
t fa
cilit
y
Che
mic
al
plan
t A
WTP
s in
Sa
itam
a, T
okyo
an
d C
hiba
pre
f.
Just
a p
H a
djus
tmen
tTo
ne ri
ver
Che
mic
al w
aste
Form
alde
hyde
fo
rmat
ion
in
chlo
rinat
ion
Hex
amin
e: P
RTR
sub
stan
ceH
exam
ine
log
Pow
=－
2.13
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Sub
mitt
ed a
list
of t
roub
ling
chem
ical
s fo
rmin
g D
BP
s in
wat
er tr
eatm
ent
Br-
Form
alde
hyde
THM
s
HM
T -4
～2
-1.2
8
0.06
0.30
0.59
-0.3
3
-1.1
3
0.76
0.06
0.34 1.62 0.69
Log
P=
20
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Est
ablis
hing
a d
atab
ase
Trea
tabi
lity
Com
mon
dat
a ba
se fo
r che
mic
als
Act
ivat
edca
rbon
adso
rptio
n
Deg
rada
tion
in
chlo
rinat
ion
Pro
duct
ion,
Det
ectio
n, T
oxic
ityO
ther
info
.
Log
Pow
Log
Dow
Hen
ry’s
law
con
stan
t
21N
atio
nal I
nstit
ute
of P
ublic
Hea
lth
Res
earc
h de
sign
for p
rom
otio
n of
pra
ctic
e
Dat
a co
llect
ion
Stat
s
Nat
iona
lsu
rvey
Join
tsu
rvey
Poin
tsu
rvey
Dat
a an
alys
is
Lab/
plan
t exp
erim
ent
Dev
elop
men
tof
ana
lytic
al
met
hods
Esta
blis
hmen
t of l
awor
ann
ounc
emen
t
Form
atio
n of
fram
ewor
k
Not
ice
Geo
logi
cal
anal
ysis
Tren
d an
alys
is
Sour
ce a
naly
sis
Pres
entin
gco
ntro
l mea
sure
s
Aca
dem
ic p
aper
Pate
nt
Trai
ning
Prac
tice
Aca
dem
ic d
evel
opm
ent
Presentation in good timing
Pres
enta
tion
WH
O g
uide
line
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
Tota
l int
ake
of c
hlor
ate
Sou
rce
iden
tific
atio
n is
im
porta
nt!!
Som
etim
es w
ater
is
the
mai
n ro
ute
of e
xpos
ure
of
hydr
ophi
lic
chem
ical
s.
Than
k yo
u !
asam
i@ni
ph.g
o.jp
Nat
iona
l Ins
titut
e of
Pub
lic H
ealth
For y
our r
efer
ence
•K
osak
aK
, Asa
miM
, Ohk
ubo
K, I
wam
oto
T, T
anak
a Y
, Kos
hino
H, E
chig
oS
, Aki
baM
. Ide
ntifi
catio
n of
a N
ew N
-Nitr
osod
imet
hyla
min
eP
recu
rsor
in S
ewag
e C
onta
inin
g In
dust
rial E
fflue
nts.
Env
iron.
Sci
. Tec
hnol
. 201
4;48
(19)
:112
43–5
0.
•A
sam
iM, Y
oshi
da N
, Kos
aka
K, O
hno
K, M
atsu
i Y. C
ontri
butio
n of
tap
wat
er to
ch
lora
te a
nd p
erch
lora
te in
take
:am
arke
t bas
ket s
tudy
, Sci
ence
of t
he T
otal
E
nviro
nmen
t. 20
13;4
63:1
99-2
08.
•A
sam
iM, K
osak
aK
, and
Kun
ikan
e S
, Bro
mat
e, C
hlor
ate,
Chl
orite
and
Per
chlo
rate
in
Sod
ium
Hyp
ochl
orite
Sol
utio
n U
sed
in W
ater
Sup
ply,
J. W
ater
Sup
ply:
Res
earc
h an
d Te
chno
logy
AQ
UA
.200
9;58
(2)1
07-1
15.
•K
osak
aK
, Asa
miM
, Kon
no Y
, Oya
M, K
unik
ane
S. I
dent
ifica
tion
of a
ntiy
ello
win
gag
ents
as
prec
urso
rs o
f N-n
itros
odim
ethy
lam
ine
prod
uctio
n on
ozo
natio
n fro
m
sew
age
treat
men
t pla
nt in
fluen
t. E
nviro
nmen
tal S
cien
ce &
Tec
hnol
ogy
2009
; 43(
14):
5236
-41.
24
