Pharmaceuticals and organic consumer chemicals in Sewage Sludge: Concentrations in Biosolids from Spain vs. the USA and China.

Damià Barceló, Bozo Zonja, Alicia Navarro and Rolf Halden

Analysis of illicit and abused drugs, pesticides and PFCs in sewage sludge

SEWAGE SLUDGE SAMPLES

15 WWTPs in 4 Mediterranean watersheds in Spain

Autumn 2010

Pooled grab samples at the end of the sewage sludge treatment– 1 Kg

BasinSTP

name

Sewage

type

Population

equivalent

Flow

(m3 day-1)Water

Treatment

Sludge

Treatment

LL

OB

RE

GA

T

LL1 D, I 196167 53500 Pre + BIO + DeN ANA+BFP

LL2 D 285666 20000 Pre + BIO ANA+CF

LL3 D 80000 23000 Pre + BIO + DeN ANA+CF

EB

RO

E1 D 776190 86141 Pre + BIO + DeN ANA+CF

E2 D 466560 51387 Pre + BIO + DeN ANA+CF

E3 D 46237 18573 Pre + BIO ANA+CF

E4 D 1200000 259200 Pre + BIO + DeN GRAV+CF

E5 D 186000 59706 Pre + BIO + DeN ANA+CF

E6 D 46847 6670 Pre + BIO ANA+CF

JU

CA

R J1 D 80000 15000 Pre + BIO ANA+CF

J2 D 232656 33584 T ANA+CF

GU

AD

AL

QU

IVIR G1 D 522000 108000 Pre + BIO ANA+CF

G2 D 30480 - Pre + BIO ANA+CF

G3 D 30000 90000 Pre + BIO ANA+CF

G4 D 1487500 135000 Pre + BIO + DeN ANA+CF

G5 D 555000 90000 T ANA+CF

GUADALQUIVIR

JUCAR

EBRO

D= domestic wastewater

I= industrial wastewater

Pre – Pretreatment: screening, sand and fat-free

BIO – Biological treatment: aeration, flocculation

and settling

DeN – denitrification;

T=Tertiary treatment: microfiltration, osmosis,

disinfection;

ANA – Anaerobic digestion

CF – centrifuge thickening and dewatering

BFP – belt filter press thickening and dewatering

GRAV – gravity thickening and dewatering

Analysis of illicit and abused drugs in sewage sludge

Mastroianni et al. J. Chromatogr. A (2013) 1322: 29-37.

• Total amounts of target abused and illicit drugs and metabolites= 138-1560 ng/g d.w.

CONCENTRATIONS FOUND IN SEWAGE SLUDGE SAMPLES

LL1 LL2 LL3 E1 E2 E3 E4 E5 E6 G1 G2 G3 G4 J1 J2

0

200

400

600

800

1200

1600

2000

ng/g

d.w

.

Cannabinoids Benzodiazepines Opioids

Amphetamine-like compounds Cocainics

Analysis of illicit and abused drugs in sewage sludge

HER, 6ACM, LSD and OH-LSD were

not detected

The most ubiquitous compounds

were METH, EDDP and THC (Log

Kow>3) (100%), followed by COC,

EPH and CBD (≥ 80%)

The most abundant compounds

were the cannabinoids (median

concentrations ranged from 78.4

ng/g d.w. (OH-THC) to 168 ng/g d.w.

(CBD)), followed by EDDP (45.6

ng/g d.w.) and METH (15.9 ng/g

d.w).

The remaining compounds

presented median concentrations

lower than 6.6 ng/g d.w.

Mastroianni et al. J. Chromatogr. A (2013) 1322: 29-37.

CO

C BECE

EPHAM M

A

MDM

AM

OR

METH

EDDP

ALP DIA

THC

CBD

CBN

OH-T

HC

0

20

40

60

80

100

%

CO

C BECE

EPHAM M

A

MDM

AM

OR

METH

EDDP

ALP DIA

THC

CBD

CBN

OH-T

HC

0.1

1

10

100

1000

ng

/g d

.w.

Median and concentration range

of target analytes in sludge samples (n=15)

Frequency of detection

of target analytes in sludge samples (n=15)

Occurrence of target analytes in sludge samples

0

10

20

30

40

50

60

70

80

90

100

Ave

rage

co

nce

ntr

atio

ns

(ng

/g d

.w.) 2010 2011334

0

5

10

15

20

25

30

Ave

rage

co

nce

ntr

atio

n (

ng

/g d

.w.)

2010 2011GUADALQUIVIR

0

10

20

30

40

50

60

70

80

90

100

Ave

rage

co

nce

ntr

atio

n (n

g/g

d.w

.) 2010 2011

0

50

100

150

200

250

300

Ave

rage

co

nce

ntr

atio

n (

ng

/g d

.w.)

2010 2011425 1235

EBRO

LLOBREGATJÚCAR

Analysis of pesticides in sewage sludge

CONCENTRATIONS FOUND IN SEWAGE SLUDGE SAMPLES

0

5

10

15

20

25

30i,p

-PFN

A

L-P

FBS

L-P

FDS

L-P

FHp

S

L-P

FHxS

L-P

FOS

PFO

DA

PFO

SA

i,p-P

FNS

PFB

A

PFD

A

PFD

oA

PFH

pA

PFH

xA

PFH

xDA

PFN

A

PFO

A

PFP

eA

PFT

eDA

PFT

rDA

PFU

dA

57 442

0

5

10

15

20

25

30

Guadalquivir

0

5

10

15

20

25

30Júcar175 81 94

0

5

10

15

20

25

30

Ebro

Llobregat1491790

Analysis of PFCs in sewage sludge

CONCENTRATIONS FOUND IN SEWAGE SLUDGE SAMPLES

0-25%

50-75%

25-50%

i,p-PFNA, i,p-PFNS, L-PFDS, PFDoA, PFHxA, PFHxDA, PFODA, PFOSA, PFTeDA, PFTrDA

L-PFBS, L-PFHpS, L-PFHxS, PFDA, PFUdA

L-PFOS, PFHpA, PFNA, PFOA, PFPeA

PFBA

Intr

od

uct

ion

• Ex

per

imen

tal•

Re

sult

s an

d d

iscu

ssio

n •

Co

ncl

usi

on

s

5%

24%

24%

48%

Analysis of PFCs in sewage sludge

OCURRENCE FREQUNCY IN THE 15 STPs

• >200 WWTPs

• Representative of 16,000+ plants

• Unbiased national estimates

• >10% of U.S. population

• >32M people

• Largest, most studied archive in the U.S.

• Anonymity through size

• E.g.: ~200,000 kg/yr of antimicrobials to US soils

Venkatesan & Halden, 2014. Environ. Sci. Pollut. Res. 22 (3), 1577-1586.

Halden, 2014. Environ. Sci. Technol. 2014, 48, 3603−3611

National Sewage Sludge Repository at ASU (NSSR)

• 38 out of 72 detected• 0.002 to 48 mg/kg dw

• TCC & TCS most abundant• 36 ± 8 & 12.6 ± 3.8 mg/kg dw

McClellan & Halden, 2010. Water Res, 44(2), 658-668.

• ∑PPCPs load in biosolids

• 210 – 250 metric t

• 2001 vs 2006/7

• =>Limited fluctuation over years

Pharmaceuticals in NSSS collected in 2001

10

• A globally shared resource at ASU

• Environmental samples

• Wastewater, sediments, sludge, surface water, plants, dust etc.

• Human samples

• Urine, blood, serum etc.

Venkatesan & Halden, 2014. Environ. Sci. Pollut. Res. 22 (3), 1577-1586.

ASU Human Health Observatory (HHO)

• 123 chemicals

• 55 potentially bioaccumulativechemicals• 93 % halogenated

• 8 priority chemicals• 3 BFRs

• 3 Surfactants

• 2 Antimicrobials

11

(12) (100) (11)

Venkatesan & Halden, 2014. Sci. Rep. 4, 3731.

Using Sewage Sludge Analysis as a Diagnostic Tool Informing Chemical Regulation

14.1 y

14.5 y

13Ag > Cu > Au > P > Fe > Pd > Mn > Zn > Ir > Al > Cd > Ti...

City of 1M people:metals & P in sludge=> $13M/y

ES&T 2015, 49:9479-9488

Where is the Value in Sludge?

US EPA

NIEHS

CDCDr. Arjun Venkatesan

Dr. Kristin McClellan

Erin Driver

AND MANY OTHERS

NIEHS R01ES015445; R01ES020889ESTCP 200914; 201122Virginia G. Piper Charitable Trust: LTR 05/01/12Johns Hopkins Center for a Livable Future

14

Thanks to:

IDAEA-CSIC team