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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 [email protected]
Acknowledgments • EHF, Environment and Health Fund, Jerusalem, Israel
• BARD, Binational Agricultural Research & Development Fund
• Ministry of Agriculture, Israel