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Journal of Contaminant Hydrol

Evaluating equilibrium and non-equilibrium transport of bromide andisoproturon in disturbed and undisturbed soil columns

S. Dousset a,, M. Thevenot b, V. Pot c, J. imunek d, F. Andreux b

a UMR 5561-Biogosciences, UFR Sciences Terre and Environnement, Universit de Bourgogne, 6 Bd Gabriel, 21000 Dijon, Franceb UMR 1229-Microbiologie et Gochimie des Sols, UFR Sciences Terre and Environnement, Universit de Bourgogne,

6 boulevard Gabriel, 21 000 Dijon, Francec UMR INRA-INA-PG-Unit Environnement et Grandes Cultures-BP 01, 78850 Thiverval-Grignon, France

d Department of Environmental Sciences, University of California, Riverside, California, USA

Received 31 July 2006; received in revised form 23 January 2007; accepted 1 July 2007Available online 17 July 2007

Abstract

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clayloam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and underunsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sievedsoil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicatecolumn experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed(structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convectivedispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model thatconsidered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of thesieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higherdegree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flowmatrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columnsusing the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transportexperiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannotbe ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similarrainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturatedsieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due to higher preferential flow and lowerfraction of equilibrium sorption sites. 2007 Elsevier B.V. All rights reserved.

Keywords: Bromide; Isoproturon; Breakthrough curves; Modeling; HYDRUS-1D

Corresponding author. Universit de Bourgogne, UFR SciencesTerre and Environnement, 6 boulevard Gabriel, 21 000 Dijon, France.Tel.: +33 3 80 39 68 88; fax: +33 3 80 39 63 87.

E-mail address: Sylvie.Dousset@u-bourgogne.fr (S. Dousset).

0169-7722/$ - see front matter 2007 Elsevier B.V. All rights reserved.doi:10.1016/j.jconhyd.2007.07.002

1. Introduction

Isoproturon is one of the most widely used herbicidesin France. It is used to control weeds in cereal crops andis one of the most frequently detected herbicides insurface and ground waters (IFEN, 2006). This herbicide

mailto:Sylvie.Dousset@u-bourgogne.frhttp://dx.doi.org/10.1016/j.jconhyd.2007.07.002

262 S. Dousset et al. / Journal of Contaminant Hydrology 94 (2007) 261276

was measured in concentrations higher than 0.1 g L1,which is the European Community Council limit forwater consumption (ECC, 1998), in numerous naturalwaters around Europe (House et al., 1997; Garmoumaet al., 1998; Spliid and Koppen, 1998). Isoproturon istherefore one of the priority substances that are moni-tored in European natural waters (OJEC, 2001).

Numerous studies have provided evidence that pref-erential flow processes are the main mechanisms ofisoproturon leaching in drained heavy clay soils (Hariaet al., 1994; Johnson et al., 1994; Brown et al., 1995;Heppel et al., 1999). Biopores (worm holes) and me-chanical pores (shrinkage cracks, and cracks resultingfrom ploughing) were identified as main vertical prefer-ential flow paths (Harris et al., 1994). Preferential trans-port of isoproturon through earthworm burrows that by-pass the soil matrix was shown at the field scale in lowerclay content soils by Zehe and Flhler (2001). Theirstudy emphasized the role of deep penetrating macro-pores interconnected with the soil surface for the oc-currence of preferential flow events.

A better understanding of mechanisms controllingpesticide behavior in macroporous structured soils withby-pass flow thus remains a current issue. Conservativetracers such as bromide, chloride and dyes are tradi-tionally used to determine the main physical transportprocesses in soils and to visualize flow pathways in fieldand/or laboratory studies (e.g., Seyfried and Rao, 1986;Andreini and Steenhuis, 1990; Flury and Flhler, 1994;Zehe and Flhler, 2001). A comparison of water flowand solute transport in sieved and undisturbed soil col-umns could help to better identify mechanisms affectingthe transport of solutes. In particular, the importanceof physical non-equilibrium transport stemming fromphysical heterogeneities (macropores) in structured soilscould be identified. The accessibility of pesticide mole-cules to reactive solid surfaces in undisturbed soils, ascompared to sieved soils, could also be assessed. Somestudies that compared transport in undisturbed anddisturbed soil columns suggest that Cl (Cassel et al.,1974; Starret et al., 1996) and atrazine (Zsolnay, 1991)move faster in undisturbed than in sieved soils. On theother hand, Veeh et al. (1994) showed that the transportof Br and chlorsulfuron is similar through undisturbedor sieved soil columns. Sadeghi et al. (2000) found afaster transport of atrazine in either the undisturbed orsieved soils depending upon the soil's physico-chemicalproperties. Finally, Griessbach et al. (1998) showed thatthe leaching of a silicone-polyether was lower in un-disturbed than in sieved soil columns. These widelycontrasting results have been reported in the literature,even for conditions where the soil texture and structure

were similar. In most studies, structured soil columnswere prepared by pushing a PVC or metallic tube intothe soil manually or with a hydraulic jack. Possible soilcompaction resulting from the use of this method cannotbe ignored and may partly explain these different obser-vations (Dousset et al., 1995).

We performed bromide and isoproturon displacementexperiments in both disturbed and undisturbed soil col-umns that were sampled from a silty clay loam soil in anintensively cultivated agricultural area (Citeaux, Cted'Or, France). In addition, the dye tracer, BrilliantBlue FCF, was used to visualize and quantify potentialmacropore pathways used by water flow in undisturbedsoil columns. Although several authors suggested that dueto its charge Brilliant Blue FCFmay sorb somewhat morestrongly than expected to the clay (Perillo et al., 1998;Kasteel et al., 2002; Nobles et al., 2004) and organiccarbon (Ketelsen and Meyer-Windel, 1999) fractions ofthe soil, Brilliant Blue FCF remains to be one of the bestdye tracers available today for identifying water flowpathways (German-Heins and Flury, 2000).

Our objectives were (i) to assess the importance ofpreferential flow on isoproturon leaching in the silty clayloam soil of Citeaux and (ii) to evaluate whether a com-parison of bromide and isoproturon leaching in disturbedand undisturbed soil columns could help identify dif-ferent processes occurring during transport. Displace-ment experiments were analyzed using multi-processsolute transport models that describe physical equilibri-um transport using the convectiondispersion equation(CDE), and physical non-equilibrium transport using thedual-permeability (DP) model that also considers chemi-cal equilibrium (instantaneous sorption) or non-equilib-rium (kinetic sorption) processes. This work contributesto our understanding of non-equilibrium reactive solutetransport processes in undisturbed and sieved laboratorysoil columns and the use of numerical models accountingsimultaneously for both physical and chemical non-equilibrium processes.

2. Materials and methods

2.1. Soils and column sampling

A silty clay loam soil (gleyic luvisol, FAO, 1998) wassampled from a fallow area of the INRA experimentalsite at Citeaux (Cte d'Or, France). Some youngalfalfa plants (Medicago sativa) were growing on thefallow soil. Three undisturbed soil column monoliths(16-cm i.d., 20-cm long) were prepared by carefullyexcavating the surrounding soil using a shovel. A 25 cm-long polyvinyl chloride (PVC) pipe with an internal

263S. Dousset et al. / Journal of Contaminant Hydrology 94 (2007) 261276

diameter of 20 cm was then placed over the soil cylinder.A minimal-expansion foam was injected into the gapbetween the soil column and the PVC pipe to fill emptyspace and thus reduce possible sidewall flow. The foamwas then allowed to harden overnight before the columnswere removed by digging under the PVC pipe. A nylonmesh was placed at the bottom of the columns to retainthe soil base. Three homogenized soil columns, werethen prepared with the same soil collected from the 020 cm horizon. The soil was first air dried and thensieved through 5-mm and, subsequently, 1-mm sieves.The soil aggregates with equivalent d