Crop irrigation with treated wastewater: Uptake of pharmaceuticals by crops, fate

and processes in arable soils

Benny Chefetz, Myah Goldstein, Tomer Malchi, Ran Yakir, Evelyn Colon de Mello, Amnon

Grossberger, Galit Tadmor, Moshe Shenker and Yitzhak Hadar

Department of Soil and Water Sciences, The Hebrew University of Jerusalem, ISRAEL

Motivation for the study

Irrigation with treated wastewater (TWW)

Pharmaceutical and Personal Care Products (PPCPs) in irrigation water (TWW)

Fate of PPCPs in soils irrigated with TWW

Uptake and translocation of PPCPs to plants

Hydroponic, greenhouse, lysimeter experiments

Conclusion

Outline

Water use by the Israeli agric. sector (1993-2012)

0%

10%

20%

30%

40%

50%

60%

70%

80% 100% = ~1 billion m3

Fresh water

Treated wastewater

Salty water, flooding Wat

er

in A

gric

ult

ure

0

10

20

30

40

50

Irrigation with Reclaimed

Wastewater (% of total)

100% = ~1 billion m3

% T

ota

l l ir

riga

tio

n w

ate

r

High quality of TWW (10/10, BOD/TSS)

Disinfection + filtration + fecal coliforms 10 MPN/100 mL unlimited irrigation

Medium quality of reclaimed WW (20/30 to 60/90, BOD/TSS)

Must have 3 barriers for irrigation

Low quality of reclaimed WW (>60/90, BOD/TSS)

Cannot be used for irrigation

The Use of TWW for Irrigation

Irrigation Stream

BOD mg/L 10 10

TSS mg/L 10 10

COD mg/L 100 70

Fecal coliforms MPN/100 mL

10 200

Dissolved oxygen mg/L 0.5< 3<

Residual chlorine mg/L 1 0.01

Total oil /hydrocarbons mg/L 1.0

pH 6.5-8.5 7.0-8.5

Total nitrogen mg/L 25 10

Ammonia mg/L 20 1.5

Total phosphorus mg/L 5 0.2

Effluent – Quality (Israel, new guidelines 2010)

Irrigation Stream

Electrical conductivity

dS/m 1.4

SAR (meq/L)0.5 5

Chloride ppm 250 400 Sodium ppm 150 200 Boron ppm 0.4

Fluoride ppm 2

Effluent – Quality (Israel, new guidelines 2010)

2/06 20/06 27/06 5/07 11/07

Caffeine 0.33 0.04 0.35 0.27 ND Lamotrigine 1.64 1.82 1.58 2.11 1.66 Metoprolol ND ND ND ND ND

Sulfapyridine 0.16 0.16 0.23 0.16 0.26 Erythromycin ND ND ND ND ND

Sildenafil ND ND ND ND ND

Sulfamethoxazole 0.34 0.27 0.30 0.35 0.43 Carbamazepine 1.02 1.03 1.06 1.32 1.05

Ketoprofen ND ND ND ND ND Bezafibrate 0.35 0.34 0.51 0.26 0.23

Clofibric acid ND ND ND ND ND Naproxen ND ND ND ND ND Diclofenac 0.54 0.64 0.47 1.01 0.85 Ibuprofen ND ND ND ND ND

Gemfibrosil ND ND ND ND ND Triclosan ND ND ND ND ND

PPCPs in secondary treated wastewater (Shafdan, 2011)

PPCPs in secondary treated

wastewater (Kiryat Gat, 2011)

30.6.11 7.7.11 7.18.11 25.7.11 16.8.11 24.8.11 30.8.11

µg/L (ppb)

Caffeine 0.7-1 0.75-75 0.19-34 0.14-0.57 0.67 0.45 0.8-0.66

Lamotrigine 1.87-1.91 0.1-1.42 0.31-0.32 0.06-1.27 0.08 0.14-0.73 0.1-0.19

Metoprolol ND ND ND 0.06 ND ND ND

Sulfapyridine ND ND ND ND ND ND ND

Erythromycin 0.14-0.16 0.14-0.17 0.17-0.19 0.14-0.22 0.14 0.11-0.18 0.17-0.26

Sildenafil 0.01 0.04-0.05 0.02-0.05 ND ND ND ND

Sulfamethoxazole 0.05-0.08 0.06-0.07 0.02 0.01 0.01 0.01-0.02 0.02-0.06

Carbamazepine 0.45-0.47 0.41-0.43 0.31-0.33 0.43-0.67 0.24 0.77-0.79 0.68-0.89

Bezafibrate 1.01-1.20 0.79-0.8 0.34-0.35 0.45-0.79 0.06 0.11-0.12 0.06-0.14

Clofibric acid ND ND ND ND ND ND ND

Ketoprofen 0.04-0.1 ND 0.03 0.02-0.03 0.04 0.01 0.01-0.04

Naproxen ND ND ND ND ND ND ND

Diclofenac 0.02 ND 0.01-0.07 ND 0.01-0.07 0.01-0.13 0.03-0.25

Ibuprofen ND ND ND 0.11 0.05 ND ND

Gemfibrozil 0.03 0.79 0.04 0.02-0.03 0.02 ND 0.01

Triclosan 0.10 ND ND 0.22-0.41 0.1-0.11 0.25-0.3 ND

Human

Sewage

Wastewater treatment plant

Agro-Ecosystem

Food-Chain

PPCPs: Fate in the Soil

Binding

Mobility

Biodegradation

Biotransformation

Uptake

Bioconcentration

PPCPs: Fate in the Soil

0 2 4 6 8 10

5

25

45

65

75

0 2 4 6 8 10 12

5

25

45

75

PPCPs concentration (ng/g soil)

De

pth

(cm

)

SMX-4

PPCPs in Loess soil irrigated with STWW

0 2 4 6 8 10 12

5

25

45

65

75

PPCPs concentration (ng/g soil)

De

pth

(cm

)

SMX-10

Caffeine 2011

Caffeine 2012

Lamotrigine 2011

Lamotrigine 2012

Carbamazepine 2011

Carbamazepine 2012

0.0

2.0

4.0

6.0

0.0

2.0

4.0

6.0

0.0

2.0

4.0

6.0

0 15 30 45 60 75 900.0

5.0

10.0

15.0

20.0

0 15 30 45 60 75 900.0

0.5

1.0

0 15 30 45 60 75 900.0

0.5

1.0

May 2011

September 2011

carbamazepine

caffeine metoprolol

sildenafil lamotrigine

sulfamethoxazole

Co

nce

ntr

atio

n (

ng

/g s

oil)

Incubation time (days)

PPCPs in soil: 90 days of incubation

0

10

20

30

40

50

60

Carbamazepine Gemfibrozil

0

10

20

30

40

Bezafibrate Naproxen

0 15 30 45 60 0

10

20

30

40

Incubation time (days)

Diclofenac

0 15 30 45 60

Ibuprofen

Co

nce

ntr

atio

n (

ng

/g s

oil)

PPCPs in the agro- environment: Uptake by crops

Hydroponic Experiments

Name Formula Uses MW

(g mol-1)

Aqueous solubility (mg L-1)

log kow pka

Carbamazepine C15H12N2O Anticonvulsant 236.27 125 2.45

Carboplatin C6H12N2O4Pt Antineoplastic 371.25 19 -0.46

Sulfapyridine C11H11N3O2S Antibacterial 249.3 268 0.35 8.43

Selected physico-chemical properties of the studied PPCPs

10043

31 230

3097

65 181

3857

2379

11711

0

2.000

4.000

6.000

8.000

10.000

12.000

CBZ SPD Pt

con

cen

trat

ion

(n

g/g

dw

) leaf stem root

Carbamazepine, Sulfapyridine and Carboplatin in cucumber organs

(Recovery ~ 10%) (Recovery ~ 18%)

(Recovery ~ 0.3%)

• Qualitative analysis of cucumber plants: LEAVES STEMS ROOTS

• Quantitative analysis of 3 samples of cucumber leaves:

[EP-CBZ] %

[EP-CBZ] ng/g

[OH-CBZ] %

[OH-CBZ] ng/g

[CBZ] ng/g

25 3448 0.6 76 13872 leaf 1

22 2046 0.9 83 9198 leaf 4

16 2137 0.5 66 13107 leaf 5

Concentrations of carbamazepine metabolites in cucumber plant parts

10,11-epoxy and/or 10,11-dihydroxyl-CBZ

Greenhouse experiments

Test plant: cucumber & tomato

Three types of soil:

1. Alluvial Soil, Beit Oren, Israel

2. Sandy Soil, Rehovot, Israel

3. Aeolian Sand, Besor, Israel

Irrigation treatments:

1. Fresh water

2. Spiked Fresh water (1ppb)

3. TWW (Shafdan – secondary treatment)

4. Spiked TWW (Shafdan) (1ppb)

PPCPs

Carbamazepine

Diclofenac

Sulfamethoxazole

Ibuprofe

n

Sulfapyridine

Ketoprofen

Naproxen

Caffeine

Lamotrigine

Metoprolol Bezafibrate

Sildenafil

Gemfibrozil

Clofibric acid

PPCPs concentrations in the cucumber plant parts

R L T0

5

10Naproxen

R L T0

5

10Ibuprofen

R L T0

5

10

15

20Gemfibrosil

R L T0

5

10

15

20Clofibric acid

R L T0

5

10

15

20Caffeine

R L T0

10

20

30

40

ng

/g (

dw

)

Lamotrigine

R L T0

10

20

30

40Metoprolol

R L T0

10

20

30

40Bezafibrate

R L T0

10

20

30

40Ketoprofen

R L T0

10

20

30

40

50Sildenafil

R L T0

1

2

3

4Sulfamethoxazole

R L T0

1

2

3

4Sulfapyridine

R L T0

100

200

300Carbamazepine

Mature leaves

Young leaves

Early fruit

Late fruit

R – Sandy Soil

L – Aeolian Sand

T – Alluvial Soil

Spiked Fresh water (1ppb)

0

1

2

3

4

Sand

Loess

Terra R

.

Naproxen

0

10

20

30

Sand

Loess

Terra R

.

Diclofenac

0

1

2

3

4

Sand

Loess

Terra R

.

Ibuprofen

0

2

4

6

Sand

Loess

Terra R

.

Gemfibrosil

0

5

10

15

Sand

Loess

Terra R

.

Bezafibrate

0

2

4

6

8

ng

PP

CP

/gL

eav

es(d

w)

Sand

Loess

Terra R

.

Clofibric acid

0

5

10

Sand

Loess

Terra R

.

Ketoprofen

0

0.5

1

Sand

Loess

Terra R

.

Triclosan

0

0.5

1

1.5

Sand

Loess

Terra R

.

Sulfamethoxazole

0

0.5

1

1.5

2

Sand

Loess

Terra R

.

Sulfapyridine

0

200

400

600

Sand

Loess

Terra R

.

Carbamazepine

0

5

10

15

20

Sand

Loess

Terra R

.

Caffeine

0

20

40

60

80

Sand

Loess

Terra R

.

Lamotrigine

0

5

10

15

Sand

Loess

Terra R

.

Metoprolol

0

5

10

15

Sand

Loess

Terra R

.

Sildenafil

FW+

TWW+

TWW

Cucumber PPCPs in Leaves

0

2

4

6

San

d

Loes

s

Terra

R.

Naproxen

0

10

20

30

San

d

Loes

s

Terra

R.

Diclofenac

0

2

4

6

San

d

Loes

s

Terra

R.

Ibuprofen

0

5

10

San

d

Loes

s

Terra

R.

Gemfibrosil

0

10

20

30

San

d

Loes

s

Terra

R.

Bezafibrate

0

5

10

ng

PP

CP

/gF

ruit

(d

w)

San

d

Loes

s

Terra

R.

Clofibric acid

0

5

10

15

20

San

d

Loes

s

Terra

R.

Ketoprofen

0

0.5

1

San

d

Loes

s

Terra

R.

Triclosan

0

0.5

1

San

d

Loes

s

Terra

R.

Sulfamethoxazole

0

0.5

1

1.5

San

d

Loes

s

Terra

R.

Sulfapyridine

0

10

20

30

San

d

Loes

s

Terra

R.

Carbamazepine

0

10

20

30

San

d

Loes

s

Terra

R.

Caffeine

0

10

20

30

San

d

Loes

s

Terra

R.

Lamotrigine

0

10

20

30

San

d

Loes

s

Terra

R.

Metoprolol

0

10

20

30

San

d

Loes

s

Terra

R.

Sildenafil

FW+

TWW+

TWW

Cucumber PPCPs in Fruits

pepper fruits cabbage leaves

Carbamazepine level: pepper fruits vs. cabbage leaves

0

10

20

30

40

50

60

ng

/gD

W pepper fruits cabbage leaves

Soil/water treatments Soil/water treatments

Consumption of crops contaminated with carbamazepine: Risks

Boy Adult

Carcinogenic

level (kg/day)

Minimal

Therapeutic

level (kg/day)

Carcinogenic

level (kg/day)

Minimal

Therapeutic

level (kg/day)

9,076 36 38,043 152 Pepper

Fruit

1,740 7 7,292 29 Chinese

Cabbage

Conclusions

PPCPs are present in reclaimed wastewater used as irrigation water PPCPs are introduced into agricultural soils some PPCPs tend to retain in the top soil layer some PPCPs can be taken up by crops.

Can PPCPs enter the food-chain!?; What are the risks (health) associated with that?

Risk assessment for mixture of chemicals! Is there a need for new regulations for water quality

(irrigation water)?

Benny Chefetz chefetz@agri.huji.ac.il

Acknowledgments • EHF, Environment and Health Fund, Jerusalem, Israel

• BARD, Binational Agricultural Research & Development Fund

• Ministry of Agriculture, Israel