Determination of in-situ biodegradation rate constants of nonylphenolic compounds in the Seine River

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Determination of in-situ biodegradation rate constants of nonylphenolic compounds in the Seine River

Mathieu Cladière, Lauriane Vilmin, Céline Bonhomme, Johnny Gasperi, Nicolas Flipo, Bruno Tassin

To cite this version:

Mathieu Cladière, Lauriane Vilmin, Céline Bonhomme, Johnny Gasperi, Nicolas Flipo, et al.. De-termination of in-situ biodegradation rate constants of nonylphenolic compounds in the Seine River. 14th EuCheMS International Conference on Chemistry and the Environment, Jun 2013, Barcelone, Spain. 2013. �hal-00862202�

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Determination of

in-situ

biodegradation

rate constants of nonylphenolic

compounds in the Seine River

Cladière Mathieu

1*

_{, Bonhomme Céline}

1

_{, Vilmin Lauriane², Gasperi Johnny}

1*

_{, Nicolas Flipo², and Tassin Bruno}

1 1

Université Paris-Est, LEESU, 94010 Créteil, France.

2 _{Centre géoscience, Mines ParisTech, Fontainebleau, France}

*_{Contact author: mathieu.cladiere@leesu.enpc.fr; gasperi@u-pec.fr}

Assessing the fate of endocrine disrupting compounds (EDC) in the environment is currently a key issue for determining their impacts on aquatic ecosystems. The 4-nonylphenol (4-NP) is a well known EDC as well as its precursors, the nonylphenol monoethoxylate (NP₁EO) and the nonylphenol acetic acid (NP₁EC). they result from the biodegradation of surfactant nonylphenol ethoxylates (NPnEO). To date, the biodegradation rate constants of nonylphenolic compounds have been mostly studied in laboratory and only Jonkers et al. (2005) focus on in-situ rate constants but in estuarine salt water. Therefore data on in-situ biodegradation of nonylphenolic compounds in river water are scarce or not up to date.

This study aims at evaluating the

in-situ

biodegradation of 4-NP, NP₁EC and NP₁EO in the Seine River downstream of Paris City.

1- INTRODUCTION

2- METHODOLOGY

Paris Se ine Flow Upstream Conflans Oise Poissy Triel _WWTP WWTP Surface water Flow Paris Se ine Flow Upstream Conflans Oise Poissy Triel _WWTP WWTP Surface water Flow

2- RESULTS

Upstream Flow; [C]

Seine River (hydrodynamic module)

K₁, K₁’, K₂, K₃

Precursor inputs Precursor inputs Precursor inputs

Conflans

[C] Poissy[C] Triel[C]

WWTP

Flow; [C] Flow; [C]Oise

ProSe model scheme

Boundary conditions Biodegradation parameters Data for calibration

Upstream Flow; [C] Upstream Flow; [C] Upstream Flow; [C]

Seine River (hydrodynamic module)

K₁, K₁’, K₂, K₃

Precursor inputs

Precursor inputs Precursor inputsPrecursor inputs Precursor inputsPrecursor inputs

Conflans [C] Conflans

[C] Conflans

[C] PoissyPoissyPoissy[C][C][C] TrielTrielTriel[C][C][C] WWTP

Flow; [C]WWTP Flow; [C]WWTP

Flow; [C] Flow; [C]Flow; [C]Flow; [C]OiseOiseOise

ProSe model scheme

Boundary conditions

Boundary conditions Biodegradation parametersBiodegradation parameters Data for calibrationData for calibration

 40 km long transect downstream of Paris city

 2 sampling campaigns: July and September 2011

 Hours of sampling estimated according to velocity of the Seine River  Samples collected in the same volume of water

 Analysis: UPLC-MS-MS  quantification of 4-NP, NP₁EC and NP₁EO

 Results  calibrating a sub-model of NPnEO biodegradation of ProSe model

 The spatial and temporal variabilities of concentrations are considered for calibration  Calibration of K₁= K₁’, K₂ and K₃based on first order kinetics equations

 Calibration of “precursor inputs” to symbolize biodegradation of NPnEO and NPnEC

The hydro-ecological ProSe model is especially design for the Seine River. Its biogeochemical module is updated to simulate the fate of nonylphenolic compounds downstream of Paris (Even et al., 1998).

July

September

oxidation NPnEC NP₁EC K₁’ K₂ K₁ 4-NP Final biodegradation ; volatilization ; adsorption K₃ NP₁EO

NPnEO oxidation NPnEC

NP₁EC K₁’ K₂ K₁ 4-NP Final biodegradation ; volatilization ; adsorption K₃ 4-NP 4-NP Final biodegradation ; volatilization ; adsorption K₃ NP₁EO NPnEO Rate constants (d-1)

Min - opt - max K₁ = K’₁ 0.05 - 0.10 - 0.15

K₂ 3.14 - 3.30 - 3.47 K₃ 2.38 - 2.50 - 2.75

Rate constants (d-1)

Min - opt - max K₁ = K’₁ 0.29 - 0.30 - 0.33 K₂ 0.08 - 0.10 - 0.14 K₃ 0.09 - 0.15 - 0.19

<

>>

<

>>

NP₁EC 0 20 40 60 80 100 120 140 710 730 750 4-NP 0 20 40 60 80 100 710 730 750 NP₁EO 0 10 20 30 710 730 750 Conce ntration s (ng/L) 1 2 3 4 1 2 3 4 1 2 3 4

Distance from source (km)

Observed profile Modelled profile 1 2 Upstream Conflans 3 4 Poissy Triel

Significant variability of biodegradation between July and September

Biodegradation rate constants are far higher

than those reported by Jonkers et al., (2005) or by Staples et al., (2001).

3- DISCUSSION / CONCLUSION

The

variability

of bacterial biomass likely

induces

the

variance of biodegradation

rate constants of

nonylphenolic compounds.

The

first-order kinetic approach

seems

reliable

to describe a

punctual state

of biodegradation but

does

not

take into account the

variabilities generated by the fluctuation of bacterial biomass.

Biodegradation rate constants are close to those reported by Jonkers et al., (2005) or by Staples et al., (2001).

Jonkers N, Laane RWPM, de Graaf C, de Voogt P. Estuarine, Coastal and Shelf Science 2005; 62: 141-160. Kisand V, Noges T. International Review of Hydrobiology 1998; 83: 205-216.

Staples CA, Naylor CG, Williams JB, Gledhill WE. Environmental Toxicology and Chemistry 2001; 20: 2450-2455.

4-NP 0 50 100 150 200 250 710 730 750 Conce ntration s (ng/L)

Distance from source (km)

NP₁EC 0 50 100 150 200 710 730 750 NP₁EO 0 10 20 30 40 50 60 710 730 750 Observed profile Modelled profile 1 2 Upstream Conflans 3 Poissy 1 2 3 1 2 3 1 2 3

Min : minimum value; opt: optimized value; max: maximum value Min : minimum value; opt: optimized value; max: maximum value

(Giger et al., 2009)

Even S, Poulin M, Gamier J, Billen G, Servais P, Chesterikoff A, Hydrobiologia 1998; 373-374: 27-45. Giger W, Gabriel FLP, Jonkers N, Wettstein FE, Kohler H-PE. Philosophical Transactions of the

Royal Society A: Mathematical, Physical and Engineering Sciences 2009; 367: 3941-3963. Campaign carried out during

an algal bloom. This algal

bloom likely induces an

increase of heterotrophic

bacterial biomass (Kisand

and Noges, 1998)

No disruption of

biogeochemical conditions of the Seine River during this campaign. The heterotrophic

bacterial biomass is

supposed to be representative

of conventional conditions of