occurrence of ppcp/edc in arizona waters and the impact of ... · and the impact of recreational...
TRANSCRIPT
Occurrence of PPCP/EDC in Arizona Waters and The Impact of Recreational Activities
Arizona State UniversitySchool of Sustainable Engineering and The Built Environment
Civil, Environmental and Sustainable Engineering
Chao-An ChiuPaul Westerhoff
Objectives
� Investigate occurrence of trace organics in multiple Arizona Waters.
� Demonstrate the seasonal effect of trace organics occurred in surface waters.
� Demonstrate the impact of water � Demonstrate the impact of water recreational activities on trace organics occurred in downstream waters.
Target compounds
Compounds name FunctionIonization
modeCompounds name Function
Ionizationmode
Acetaminophen NSAID ESI + Naproxen NSAID ESI -
Caffeine stimulant ESI + Oxybenzone Sunscreens ESI +
Carbamazepine anticonvulsant ESI + Pentoxifylline antiplatelet drug ESI +
Cotinine metabolite of nicotine ESI + Primidone Anticonvulsant ESI +
DEET insect repellent ESI + Sucralose artificial sweetener ESI -
Diazepam anxiolytic ESI + Sulfamethoxazole antibiotic ESI +
Diclofenac NSAID ESI - TBBA flame retardant ESI -
Dilantin antiepileptic ESI - Triclosan antibiotic ESI -
Erythromycin antibiotic ESI + Trimethoprim antibiotic ESI +
Fluoxetine antidepressant ESI + Estradiol sex hormone APCI
Hydrocodone narcotic analgesic ESI + Ethinyl Estradiol estrogen APCI
Ibuprofen NSAID ESI - Progesterone steroid hormone APCI
Meprobamate anxiolytic ESI + Testosterone steroid hormone APCI
Analytical Scheme
� Filtration using 0.75µm (GF/F) filter paper.
� Solid phase extraction (Oasis HLB) @ ASU
� Analysis at ADHS � Analysis at ADHS (LC/MS/MS)
� Isotope spiking for recovery correction
� Quality control – lab blank, field blank and duplication.
Arizona Potential EDC/PPCP Sources
� Colorado River
� Wastewater discharges into rivers and groundwater
� Leaking septic systems
� Houseboats & direct contact (recreation)
Overview of PPCP/EDC in AZ waters
Source< 2 ng/L
& ≤≤≤≤ Blank2 to 10 ng/L
10 to 20 ng/L
20 ng/L to 1 ug/L > 1 ug/L
Ground water at recharge site
Steroids and others
Acetaminophen, caffeine, DEET, erythromycin,
meprobamate oxybenzone, pentoxifylline
NoneSulfamethoxazole,
sucralose (in one site)None
SRP waters (Verde River &
Salt River)
Steroids and others
Sucralose, sulfamethoxazole, acetaminophen, cotinine,
dilantin,
Caffeine, DEET
Oxybenzone None
CAP Canal from Steroids and
Sulfamethoxazole, oxybenzone, meprobamate,
DEET, cotinine, dilantin, Caffeine,Sucralose None
CAP Canal from Colorado River
Steroids and others
DEET, cotinine, dilantin, carbamazepine,
acetaminophen, primidone, estradiol
Caffeine,triclosan
Sucralose None
Activated sludge WWTP effluent
with nitrification
Steroids and others
Acetaminophen, ibuprofen, diazepam, pentoxifylline
Cotinine
Caffeine, naproxen, oxybenzone, TBBA,
carbamazepine, hydrocodone, meprobamate,
sulfamethoxazole, DEET, erythromycin, trimethoprim, primidone, dilantin, triclosan,
diclofenac, sucralose, fluoxetine
None
Raw wastewater None None
Diazepam, ethinyl
estradiol, progestero
ne
Testosterone, hydrocodone, pentoxifylline, erythromycin,
trimethoprim, primidone, fluoxetine carbamazepine,
dilantin, diclofenac
Ibuprofen, naproxen, triclosan, sucralose, acetominophen,
caffeine, cotinine, oxybenzone, DEET, meprobamate, TBBA,
sulfamethoxazole
Surface Waters
� CAP Canal, Salt River, and Verde River�> 90% samples were measured with PPCP/EDC
presented.�Progesterone was not detected in any of them.�Concentrations were low (less than 50 ng/L).�Oxybenzone and sucralose exceeded 300 ng/L
during the period.�15/26 compounds were prevalent (>50%
occurrences).�Caffeine, DEET, Sucralose and oxybenzone
were detected in most samples (>90% occurrences)
250250250250
300300300300
350350350350
400400400400M
onth
ly T
otal
Con
cent
ratio
n (n
g/L)
Mon
thly
Tot
al C
once
ntra
tion
(ng/
L)M
onth
ly T
otal
Con
cent
ratio
n (n
g/L)
Mon
thly
Tot
al C
once
ntra
tion
(ng/
L)
SucraloseSucraloseSucraloseSucraloseOxybenzoneOxybenzoneOxybenzoneOxybenzonethe restthe restthe restthe rest
Seasonal effect on PPCP in surface waters
250250250250
300300300300
350350350350
400400400400M
onth
ly T
otal
Con
cent
ratio
n (n
g/L)
Mon
thly
Tot
al C
once
ntra
tion
(ng/
L)M
onth
ly T
otal
Con
cent
ratio
n (n
g/L)
Mon
thly
Tot
al C
once
ntra
tion
(ng/
L)
SucraloseSucraloseSucraloseSucraloseOxybenzoneOxybenzoneOxybenzoneOxybenzonethe restthe restthe restthe rest
May to Sep
Others
May to Sep
0000
50505050
100100100100
150150150150
200200200200
R3R3R3R3 R10R10R10R10 R25R25R25R25
Mon
thly
Tot
al C
once
ntra
tion
(ng/
L)M
onth
ly T
otal
Con
cent
ratio
n (n
g/L)
Mon
thly
Tot
al C
once
ntra
tion
(ng/
L)M
onth
ly T
otal
Con
cent
ratio
n (n
g/L)
75%
60%
86%
16%52% 10%
0000
50505050
100100100100
150150150150
200200200200
R3R3R3R3 R10R10R10R10 R25R25R25R25
Mon
thly
Tot
al C
once
ntra
tion
(ng/
L)M
onth
ly T
otal
Con
cent
ratio
n (n
g/L)
Mon
thly
Tot
al C
once
ntra
tion
(ng/
L)M
onth
ly T
otal
Con
cent
ratio
n (n
g/L)
75%
60%
86%
16%52% 10%
Others
Others
May to Sep
CAP canal Salt River Verde River
Water Treatment Plant
�WTP in Tempe�Only Caffeine, DEET, Sucralose and
oxybenzone were detected >10 ng/L in some WTP influent samples.
�11/26 compounds remained in finished water �11/26 compounds remained in finished water (1~5 ng/L)
�Chlorination shows further oxidation on some compounds, especially oxybenzone.
Removal efficiency in WTP
(Uint: ng/L)
Raw Water Sedimentation Disinfection % Removal
Oxybenzone 43 25 0 100%
Caffeine 10 7 5 52%
Sucralose 10 4 4 61%
DEET 6 3 3 46%
Acetaminophen 2 2 2 <1%
Erythromycin 1 1 1 <1%
Cotinine 1 1 1 <1%
Meprobamate 1 1 1 <1%
Pentoxifylline 1 1 1 <1%
Sulfamethoxazole 1 1 0 79%
TBBA 1 1 0 17%
Seasonal effect on PPCP/EDC in drinking water
80
100
120
140
mon
thly
tota
l con
cent
ratio
n (n
g/L)
OxybenzoneCaffeineSucraloseDEETrest
10%
4%
27%
May to Sep
May to Sep
0
20
40
60
80
SPTin SPTout SPTCl2
mon
thly
tota
l con
cent
ratio
n (n
g/L)
59%
10%
29%
17%
26%
27%
56%
11%
3%
31%
25%12%
17% 47%
11%12%12%65%
25%12%17%
47%
Others
May to
SepOthers
Others
WTP inf WTP sed. WTP Cl2
Wastewater Treatment Plant
�WWTP�12 out of 26 compounds were detected >1
µg/L; acetaminophen, caffeine, ibuprofen, and naproxen were >10 µg/L.
�Several compounds (caffeine, DEET, �Several compounds (caffeine, DEET, oxybenzone, ibuprofen, meprobamate, and triclosan) shows increasing trend in raw wastewater during summer.
�Removal efficiency of PPCP/EDC is not necessarily K ow correlated in WWTP.
WWTP removal efficiency of PPCP/EDC
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
conc
entr
atio
n (n
g/L)
60%
80%
100%
120%
perc
enta
ge r
emov
al
MESAin MESAUV percentage removalInffluent Effluent
1.E-02
1.E-01
1.E+00
1.E+01
1.E+02
Ace
tam
inop
hen
Caf
fein
e
Nap
roxe
n
Ibup
rofe
n
Oxy
benz
one
Suc
ralo
se
Sul
fam
etho
xazo
le
Cot
inin
e
Tric
losa
n
DE
ET
Mep
roba
mat
e
Trim
etho
prim
Prim
idon
e
TB
BA
Car
bam
azep
ine
Dila
ntin
Dic
lofe
nac
Ery
thro
myc
in
Hyd
roco
done
Flu
oxet
ine
Tes
tost
eron
e
Pen
toxi
fylli
ne
Est
radi
ol
Eth
inyl
Est
radi
ol
Pro
gest
eron
e
Dia
zepa
m
conc
entr
atio
n (n
g/L)
0%
20%
40%
60%
perc
enta
ge r
emov
al
Water Recreation Area
�Salt River and Slide Rock recreation area� Samples were collected hourly in one day
during summer� Caffeine, DEET, and acetaminophen � Caffeine, DEET, and acetaminophen
increased along time (up to 120 ng/L)� Oxybenzone was detected >1 µg/L� Most of the sources for these detected
PPCPs are from skin-applied products (sunscreen, insect repellent) rather than oral-applied drugs.
Salt River Recreation
Slide Rock
0
20
40
60
80
100
120
9:00 10:00 13:00 14:00 15:00 16:00 17:00
conc
entr
atio
n (n
g/L)
0
1000
2000
3000
4000
5000
6000
7000
oxyb
enzo
ne c
onc
(ng/
L)
Acetominophen
Caffeine
DEET
Oxybenzone
0
50
100
150
200
250
11:00 12:00 13:00 14:00 15:00 16:00 17:00
conc
entr
atio
n (n
g/L)
0
500
1000
1500
2000
2500
oxyb
enzo
ne c
onc
(ng/
L)
Acetaminophen
Caffeine
DEET
Meprobamate
sucralose
Oxybenzone
2008, Summer, Salt River 2009, Summer, Slide Rock
9:00 10:00 13:00 14:00 15:00 16:00 17:00 11:00 12:00 13:00 14:00 15:00 16:00 17:00
0
5
10
15
20
25
30
35
40
45
9:00 10:00 11:00 12:00 13:00 14:00 15:00 16:00 17:00 18:00
conc
entr
atio
n (n
g/L
)
0
500
1000
1500
2000
2500
oxyb
enzo
ne c
onc
(ng/
L)
AcetaminophenCaffeineDEETMeprobamatesucraloseOxybenzone
2009, Summer, Salt River
GRUSP Measuring Wells
� 13 out of 26 compounds were detected in three measuring wells.
� Most of the detected concentrations are low (< 5 ng /L)
� Acetaminophen, caffeine, DEET, Sulfamethoxazole, Sucralose, and Erythromycin were constantly present in ground water system.in ground water system.
● Sulfamethoxazole was detected up to 200 ng/L in MW#3.
PPCP/EDC occurrence in Phoenix water supply area
� PPCP/EDC existing in surface water system might increase health risk for drinking water management.
� Water recreation and lakes from upstream could be important sources of these PPCP/EDC present in canal system of Phoenix area.canal system of Phoenix area.
� Seasonal effect on different surface waters might influence raw water quality of WTP during source water switch by SRP.
� Tracking the occurrences and fate of these PPCP/EDC in drinking water system is important for water management of metropolitan Phoenix.
Acknowledgement
� Salt River Project, Arizona� Arizona Department of Health Services� Central Arizona Project� City of Tempe, City of Phoenix, and City
of Mesaof Mesa� Pierre Herckes, Chemistry and
Biochemistry, ASU� Marisa Masles