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