1Application of soil amendments toenhance ketoprofen attenuation invegetation filters: lab-scale
experiments and reactive
transport modelling
Raisa G. Salvi-Tagaa, Raffaella Meffeb, Virtudes
Martínez-Hernándezb, Irene de Bustamantea, ba Department of Geology, Geography and Environment, University of Alcala,

Spain
Alcalá de Henares, Spain

Alcalá de Henares,b IMDEA Water Institute,Prague, April 21st, 2023

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

2Outline
Introduction and Objectives
Methodology
Results and Discussion
Conclusions

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

3

Pharmaceuticals

Fertilizers

Introduction

Introduction
Microplastics

Personal Care Products

Intense consumption and discharge
into the environment
Incomplete removal in wastewater
treatment plants (WWTPs)

Contaminants of Emerging Concern
Found worldwide in surface water,
groundwater, sediment and soil
PFAS

April 21st, 2023

Plasticizers

Disinfection By-products

Nanomaterials

Pose a significant risk to humans
and ecosystems

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport ProblemsVegetation Filters (VFs), nature-based
solutions for wastewater treatment

Introduction
Removal efficiency of the anti-inflammatory
KETOPROFEN reached only 55.4 %Pose a higher threat forgroundwater contamination

Soil amendments (such as woodchips) canenhance the nutrient removal

April 21st, 2023

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Introduction

4Objectives
 Assess whether woodchip amendments
to the soil of a VF are able to enhance
the ketoprofen removal in the water
infiltrating through the vadose zone andrecharging the aquifer; Develop flow and transport models todescribe and compare the transport ofketoprofen though the unsaturated
zone of an unamended FV and throughthe same soil amended with woodchips.

April 21st, 2023

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Objectives

56Methodology
10 cm

10 cm

Poplarwoodchips

April 21st, 2023

35 cm

35 cm
Glass filter plate

18 cm

18 cm

Glass filter plate

VF soil

3 cm

VF soil

3 cm

Glass fragments

2 cm

12 cm

Glass fragments

4 cm

Column WS

10 cm

Column S VF soil of moderately coarse
texture (sandy loam), neutral(pH of 7.64 ± 0.08) with a notvery high organic mattercontent (1.47 ± 0.08%);
 Tracer test: 10 g/L of NaCl(single pulse); Daily additions (pulse of 1 s) of
50 mL of a synthetic
wastewater with aconcentration of 1 mg/L ofketoprofen; Ketoprofen concentrations
were measured regularly at thecolumns’ effluent during 62
days.

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Methodology

Experimental set-up: Soil column experiments

7Methodology

HYDRUS-1D Numerical Modelling Soil Layer:Van Genuchten-Mualem with no hysteresis; Woodchip layer: Dual-porosity (MIM);
 Water flow boundary conditions: Upper: Atmospheric BC with Surface Layer;
 Lower: Seepage Face BC;
 Solute transport boundary conditions:

STAGE 1: CONSERVATIVE TRANSPORT (TRACER)STAGE 2: REACTIVE TRANSPORT

April 21st, 2023

 Upper: Concentration flux BC;
 Lower: Zero concentration gradient; Difference between applied and recollected effluent: daily
average evaporation in Time-Variable BC; Daily average bottom concentration: daily sum(cvBot)/sum(vbot); Linear sorption and first-order degradation kinetic;
 Molecular diffusion was not neglected.
Column S

Soil layer: Ks, αL, Dw

Column WS

Woodchip layer: θsmo, θsim,α, n, ω, Ks, αL, Dw

Column S

Soil layer: Kd, µw

Column WS

Soil layer: µw
Woodchip layer: Kd, µw

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Methodology

 Hydraulic model:

8Methodology

HYDRUS-1D Numerical Modelling
Value
Parameter

ColumnSoilValue

Column WS

Parameter

Column S

Woodchip
layer

Soil layer

Length

18.0 cm

10.0 cm

18.0 cmθr

0.0581-0.0581

α0.0173 cm-1-

0.0173 cm-1

n1.4467-

1.4467I

0.5(1)

0.5

0.5

θs

0.42070.85 (θsmo+ θsim)

0.4207

Soil layer: Rosetta estimation

Column WS
Column S

Woodchip
layer

Soil layerρ

1.41 g cm-3

0.21 g cm-3

1.41 g cm-3

Upper h-18.0 cm-28.0 cm

Lower h0.0 cm

0.0 cmFlux (pulse:1 second
every 24 hours)

0.637 cm s-1

0.637 cm s-1

NaCl concentration

0.171 mmol cm-30.171 mmol cm-3

Ketoprofen
concentration

3.94E-6 mmol cm-3

3.94E-6 mmol cm-3

Soil/woodchip
Initialconditions(1): Mualem, 1976.

April 21st, 2023

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Methodology

Model parameters

9Results and Discussion

Water flow and tracer transport

PARAMETER

800

Cl- Concentration (mg L-1)

700

500

Woodchip Layer

Ks

3.11E-05

2.18E-02

cm s-1αL

1.08E-02

7.48E-01

cmPARAMETERFit Column S (R²=0,999)
Data Tracer Column S

400

Fit Column WS (R²=0.986)
Data Tracer Column WS

300
200100UNIT

Soil Layer

Dw

600

VALUE

cm2 s-1

2.13E-05
VALUE
Woodchip Layer

UNIT

θsmo

2.93E-01

cm3 cm-3

θsim

5.57E-01

cm3 cm-3

α2.00E-02cm-1n

1.40E+00-ω

3.54E-07

s-1

TOTAL OUTFLOW
EXPERIMENTAL SIMULATED RMSE
VOLUME

00April 21st, 2023

510152025Time (d)3035404550

Column S

2,032.34 mL

2,033.25 mL 4.53 mL

Column WS

2,016.97 mL

1,994.66 mL 4.87 mL

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Results

Cl- Breakthrough Curves

Ketoprofen reactive transport

SCENARIO Kd (L kg-1) µw (d-1)

Column S Breakthrough Curve - Kd Variation
Area3
Area
Area2
DataFit
Kd+10%
Kd+20%
Kd-10%
Kd-20%

0800

600% VARIATION
Kd% VARIATIONµw

Fit

6.47E-01

5.41E-02 0.9852

17.04--

Kd +10%7.11E-01

4.70E-02 0.9686

27.00

10%-13.0%

Kd +15%

7.44E-01

4.08E-02 0.9569

31.84

15%-24.5%Kd +20%

7.76E-01

3.39E-02 0.9474

32.2320%-37.4%

Kd -10%5.82E-01

7.08E-02 0.9847

17.24-10%

30.9%

Kd -15%5.50E-01

7.54E-02 0.9822

18.59-15%

39.4%

Kd -20%5.17E-01

8.03E-02 0.9715

23.77-20%

48.5%

400

0Area3500

Area2
Data

300

400
300

Fit
Kd+10%
Kd+20%

200

200

Kd-10%
Kd-20%

100

100
0010

April 21st, 2023

20304010Area

Ketoprofen Concentration (µg L-1)

Ketoprofen Concentration (µg L-1)

700

RMSE(µg L-1)

Results

900

R250

60 70 80Time (day)90

100 110 120 130 140

0010203040Time (day)5060

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Ketoprofen reactive transport

SCENARIO Kd (L kg-1) µw (d-1)

Column S Breakthrough Curve - µw Variation
Area3

800

Area2
Data
Fit
uw +10%600

uw-10%uw+20%

500

RMSE(µg L-1)

% VARIATION
Kd% VARIATIONµw

Fit

6.47E-01

5.41E-02 0.9852

17.04--µw +10%6.41E-01

5.95E-02 0.9856

17.83-0.8%

10.0%µw +15%

6.29E-01

6.22E-02 0.9848

17.47

-2.7%

15.0%

µw +20%6.17E-01

6.49E-02 0.9846

17.37

-4.6%

20.0%

µw -10%6.92E-01

4.87E-02 0.9755

20.47

7.0%

-10.0%µw -15%

7.04E-01

4.60E-02 0.9720

22.07

8.8%

-15.0%µw -20%7.11E-01

4.33E-02 0.9673

24.78

9.9%

-20.0%

11400

uw-20%
Ketoprofen Concentration (µg L-1)

300

400

300

Results

Ketoprofen Concentration (µg L-1)

700

R2

200

200

100

100

000April 21st, 2023

102030405060 70 80
Time (day)90

100 110 120 130 140010203040Time (day)5060

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Ketoprofen reactive transport

Kd (L kg-1)
MODEL

700

80Column S - Data

Column SColumn S - Fit

70

Column WS - Data
Column WS - Fit (1)60Column WS - Fit (2)500Column WS - Fit (3)Column WS - Fit (4)

50400
40300
30200

20100

Ketoprofen Concentration - Column WS (ug L-1)

Ketoprofen Concentration - Column S (ug L-1)

600Column
WSSoil Woodchip Soil Woodchip
Layer
Layer
LayerLayer
6.47E-01

0020406080
Time (d)April 21st, 2023

100

120

140

5.41E-02-0.985

17.03616.47E-01 1.03E+01 2.25E-01 2.25E-01

0.951

1.317

26.47E-01 1.03E+01 6.17E-02 7.47E-01

0.953

1.232

36.47E-01 1.03E+01 3.19E-01 0.00E+00

0.943

1.417

46.47E-01 1.03E+01 0.00E+00 9.70E-01

0.951

1.311

12

1: Identical degradation rates within the Column WS soil andwoodchip layers.
2: Different degradation rates within the Column WS soil andwoodchip layers.
3: No degradation within the Column WS woodchip layer.
4: No degradation within the Column WS soil layer.

100-R2RMSE(ug L-1)

Column WS

MODEL

KETOPROFENREMOVAL (%)

Column S

36.53%
196.36%296.60%396.12%496.27%7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Results

Ketoprofen breakthrough curves – Column S x Column WSμw (d-1)

13Conclusions
 Excellent fits (R2 > 0,95) were obtained for all models, allowing to complete breakthrough curves ofketoprofen that were experimentally monitored up to day 62;
 The transport model with a linear sorption equilibrium model and a first-order degradation kinetic
successfully simulates ketoprofen breakthrough curves in both Columns S and WS;
 Low values of Kd and µw obtained for the soil layer indicates that the occurrence of processes of sorption
and biodegradation in soil for ketoprofen is limited, when compared to other pharmaceuticals in the literature; The fitted breakthrough curves modeled an average removal of, respectively, 37% and 96% of ketoprofen inColumns S and WS, corroborating the effectiveness of the use of the woodchip amendment for the treatment ofketoprofen in Vegetation Filters.

April 21st, 2023

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems

Conclusions

 Kd and µw obtained for the woodchip layer are 1 order of magnitude higher than the same parameters in soil,
indicating that the presence of woodchips enhances the processes of sorption and biodegradation in the profile,
but biodegradation plays a more relevant role in terms of natural attenuation;

14THANK YOU!
Raisa Gabriela Salvi Taga
PhD Student
gabriela.salvi@edu.uah.esApril 21st, 2023

7th International HYDRUS Conference
HYDRUS Software Applications to Subsurface Flow and Contaminant Transport Problems