M Hussein

N Assadi
email: assadi@aquarius.mp.es.osaka-u.ac.jp

Dorian A H Hanaor

The effects of copper doping on photocatalytic activity at (101) planes of anatase TiO2: A theoretical study

Keywords: Ab-initio, Copper dopant, TiO2, Water adsorption

Copper dopants are varyingly reported to enhance photocatalytic activity at titanium dioxide surfaces through uncertain mechanisms. In order to interpret how copper doping might alter the performance of titanium dioxide photocatalysts in aqueous media we applied density functional theory methods to simulate surface units of doped anatase (101) planes. By including van der Waals interactions, we consider the energetics of adsorbed water at anatase surfaces in pristine and copper doped systems. Simulation results indicate that copper dopant at anatase (101) surfaces is most stable in a 2+ oxidation state and a disperse configuration, suggesting the formation of secondary CuO phases is energetically unfavourable. In agreement with previous reports, water at the studied surface is predicted to exhibit molecular adsorption with this tendency slightly enhanced by copper. Results imply that the enhancement of photoactivity at anatase surfaces through Cu doping is more likely to arise from electronic interactions mediated by charge transfer and inter-bandgap states increasing photoexcitation and extending surface-hole lifetimes rather than through the increased density of adsorbed hydroxyl groups.

1.

Introduction: Transition metal doping of titanium dioxide photocatalysts is often carried out with the aim of enhancing photocatalytic activity through improved photoexcitation and/or reduced electron-hole recombination [START_REF] Wilke | The influence of transition metal doping on the physical and photocatalytic properties of titania[END_REF][START_REF] Zhang | Enhanced photocatalytic activity for titanium dioxide by comodification with copper and iron[END_REF]. Despite an increasingly large number of investigations into these materials, applied transition metal doped TiO2 photocatalysts are yet to find applications. The entanglement of multiple surface and bulk effects and non-equilibrium behaviour encumber experimental investigations into doped systems and consequently, the mechanisms through which transition metal doping may enhance photocatalytic activity of titanium dioxide remain unclear, limiting progress towards the optimisation and future utilisation of such materials. Moreover, a number of studies have found an impairment to photocatalytic activity may arise from the addition of such dopants, which may act as exciton recombination centres [START_REF] Wetchakun | Synthesis and characterization of transition metal ion doping on the photocatalytic activity of TiO2 nanoparticles[END_REF][START_REF] Bahnemann | Photodestruction of dichloroacetic acid catalyzed by nano-sized TiO2 particles[END_REF].

Copper in particular is widely utilised as a dopant in TiO2 in efforts to enhance photocatalytic performance. Relative to pristine materials, Cu doped titanium dioxide (Cu-TiO2) is commonly reported to exhibit improved electron-hole separation with photoexcitation. Although dopant surface concentration would be a more relevant parameter, experimental studies have found improvements in photocatalytic activity to be optimised at Cu dopant levels between 0.1-2 at% [START_REF] Xia | Structure and photocatalytic properties of copperdoped rutile TiO2 prepared by a lowtemperature process[END_REF][START_REF] Li | Role of Surface/Interfacial Cu 2+ Sites in the Photocatalytic Activity of Coupled CuO-TiO2 Nanocomposites[END_REF][START_REF] Morikawa | Enhanced photocatalytic activity of TiO2-xNx loaded with copper ions under visible light irradiation[END_REF][START_REF] Song | Photocatalytic activity of Cu/TiO2 with oxidation state of surface-loaded copper[END_REF][START_REF] Zhang | Copper doping in titanium oxide catalyst film prepared by DC reactive magnetron sputtering[END_REF][START_REF] Song | Photocatalytic Activity of (Copper, Nitrogen)-Codoped Titanium Dioxide Nanoparticles[END_REF][START_REF] López | Photophysical and photocatalytic properties of nanosized copper-doped titania sol-gel catalysts[END_REF].

Most laboratory studies conducted towards TiO2 photocatalysis have utilised powder form material, predominantly in the anatase phase, although the fabrication of thin films and rutile materials is also often undertaken [START_REF] Hanaor | Sorrell Morphology and photocatalytic activity of highly oriented mixed phase titanium dioxide thin films[END_REF][START_REF] Hanaor | Sand Supported Mixed-Phase TiO2 Photocatalysts for Water Decontamination Applications[END_REF][START_REF] Schneider | Understanding TiO2 photocatalysis: mechanisms and materials[END_REF].

Copper dopant behaviour in TiO2 is strongly linked to synthesis parameters and the diverse methods employed in materials fabrication and analyses have understandably yielded varied findings. Experimental studies have observed diverse Cu speciation in doped TiO2 with a majority of studies reporting the presence of copper dopant in a Cu 2+ valence. These species are frequently reported to substitute for Ti 4+ to give a solution phase with the composition CuxTi1-xO2 and an increased lattice density of oxygen vacancies [START_REF] Xia | Structure and photocatalytic properties of copperdoped rutile TiO2 prepared by a lowtemperature process[END_REF][START_REF] Li | Role of Surface/Interfacial Cu 2+ Sites in the Photocatalytic Activity of Coupled CuO-TiO2 Nanocomposites[END_REF][START_REF] Song | Photocatalytic Activity of (Copper, Nitrogen)-Codoped Titanium Dioxide Nanoparticles[END_REF][START_REF] Sivalingam | Photocatalytic degradation of various dyes by combustion synthesized nano anatase TiO2[END_REF][START_REF] Nian | Structural feature and catalytic performance of Cu species distributed over TiO2 nanotubes[END_REF][START_REF] Hanaor | Review of the anatase to rutile phase transformation[END_REF], and reportedly may also occupy interstices in anatase [START_REF] López | Photophysical and photocatalytic properties of nanosized copper-doped titania sol-gel catalysts[END_REF][START_REF] Grunin | EPR of Cu 2+ and radiation centres in anatase (TiO2)[END_REF]. In addition to solid solutions, Cu 2+ is widely found to exist in crystalline or amorphous CuO nanoclusters and surface localised Cu(OH)2 in doped TiO2 [START_REF] Xia | Structure and photocatalytic properties of copperdoped rutile TiO2 prepared by a lowtemperature process[END_REF][START_REF] Li | Role of Surface/Interfacial Cu 2+ Sites in the Photocatalytic Activity of Coupled CuO-TiO2 Nanocomposites[END_REF][START_REF] Morikawa | Enhanced photocatalytic activity of TiO2-xNx loaded with copper ions under visible light irradiation[END_REF][START_REF] Zhang | Copper doping in titanium oxide catalyst film prepared by DC reactive magnetron sputtering[END_REF][START_REF] Francisco | X-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and x-ray diffraction characterization of CuO-TiO2-CeO2 catalyst system[END_REF]. Less common than Cu 2+ , the presence of monovalent Cu + is also reported, both in substitutional positions as well as in Cu2O clusters [START_REF] Song | Photocatalytic activity of Cu/TiO2 with oxidation state of surface-loaded copper[END_REF][START_REF] López | Photophysical and photocatalytic properties of nanosized copper-doped titania sol-gel catalysts[END_REF][START_REF] Colón | Cu-doped TiO2 systems with improved photocatalytic activity[END_REF]. Reports suggesting the absence of a CuO or Cu2O phase often rely on XRD data, and it should be noted that such results do not necessarily preclude the existence of amorphous or fine secondary oxide precipitates. Finally, copper dopant as metallic Cu 0 species is observed to arise even when fired in air in the absence of a reducing agent and is likely to play a role similar to Au or Ag dopant nanoclusters [START_REF] Song | Photocatalytic activity of Cu/TiO2 with oxidation state of surface-loaded copper[END_REF][START_REF] López | Photophysical and photocatalytic properties of nanosized copper-doped titania sol-gel catalysts[END_REF].

The experimental evidence for the enhancement of photocatalytic activity in TiO2 through copper doping is inconclusive, and diverse mechanisms are reported. Enhanced activity is most often understood to be driven by reduced charge carrier recombination in Cu-TiO2 materials. This has been reported to arise as the result of photo-generated electrons facilitating the reduction Cu 2+ + e -→ Cu + , thus extending the valence band hole lifetimes at surfaces, which are able to react with adsorbed species to form active radicals [START_REF] Xia | Structure and photocatalytic properties of copperdoped rutile TiO2 prepared by a lowtemperature process[END_REF][START_REF] Li | Role of Surface/Interfacial Cu 2+ Sites in the Photocatalytic Activity of Coupled CuO-TiO2 Nanocomposites[END_REF]. However, reports that Cu + and Cu 0 enhance photo-activity more effectively than Cu 2+ are in disagreement with this mechanism [START_REF] Song | Photocatalytic activity of Cu/TiO2 with oxidation state of surface-loaded copper[END_REF][START_REF] Colón | Cu-doped TiO2 systems with improved photocatalytic activity[END_REF]. Alternatively, the presence of a CuO or Cu2O phase in may improve exciton lifetime through electron capture in the secondary phase [START_REF] Liu | Cu(II) oxide amorphous nanoclusters grafted Ti 3+ self-doped TiO2: an efficient visible light photocatalyst[END_REF][START_REF] Hu | Effective water splitting using CuOx/TiO2 composite films: Role of Cu species and content in hydrogen generation[END_REF] or enhance activity through an increased surface area [START_REF] Xia | Structure and photocatalytic properties of copperdoped rutile TiO2 prepared by a lowtemperature process[END_REF][START_REF] Francisco | Activity and characterization by XPS, HR-TEM, Raman spectroscopy, and BET surface area of CuO/CeO2-TiO2 catalysts[END_REF]. Metallic clusters are understood to enhance photoactivity by expediting charge transfer with adsorbed species [START_REF] Song | Photocatalytic activity of Cu/TiO2 with oxidation state of surface-loaded copper[END_REF] while band-gap narrowing induced by copper cations may extend the range of wavelengths that are utilised in photocatalysis [START_REF] Song | Photocatalytic Activity of (Copper, Nitrogen)-Codoped Titanium Dioxide Nanoparticles[END_REF][START_REF] Choudhury | Defect generation, d-d transition, and band gap reduction in Cu-doped TiO2 nanoparticles[END_REF]. Above a certain threshold, increasing the concentration of Cu dopant is often reported to bring about a diminishment in photocatalytic activity through a combination of enhanced recombination and shading [START_REF] Li | Role of Surface/Interfacial Cu 2+ Sites in the Photocatalytic Activity of Coupled CuO-TiO2 Nanocomposites[END_REF][START_REF] Zhang | Copper doping in titanium oxide catalyst film prepared by DC reactive magnetron sputtering[END_REF].

The diversity in the reported behaviour of Cu dopants and their effects on photocatalytic activity stems largely from diverse materials synthesis methods that result in Cu dopant in non-equilibrium sites, as well as from the diverse approaches through which photocatalytic activity is assessed. As with other dopants, the effect of a copper dopant on photoactivity in TiO2 is likely to strongly depend on the experimental conditions used [START_REF] Subramanian | Influence of metal/metal ion concentration on the photocatalytic activity of TiO2-Au composite nanoparticles[END_REF]. Additionally, as copper nanostructures are themselves known to act as catalysts for oxidative reactions, decoupling the secondary phase activity from the observed titanium dioxide driven photocatalysis may be problematic from experimental point of view.

In addition to the material interactions of transition metal doping, the speciation of adsorbates at terminated oxide interfaces plays a critical role in controlling the performance of applied photocatalysts and has rarely been considered in computational studies. Photocatalysed phenomena at TiO2 surfaces are most often mediated through adsorbed water and the associated intermediate radical species that arise through photocatalysed redox reactions. Water at TiO2 surfaces in general and anatase surfaces in particular is known to be present though associative (molecular) and dissociative adsorption [START_REF] Bandura | Adsorption of Water on the TiO2 (Rutile) (110) Surface: A Comparison of Periodic and Embedded Cluster Calculations[END_REF][START_REF] Walle | Mixed Dissociative and Molecular Water Adsorption on Anatase TiO2(101)[END_REF][START_REF] Cheng | Hydroxide Ions at the Water/Anatase TiO2(101) Interface: Structure and Electronic States from First Principles Molecular Dynamics[END_REF]. Considering the likely mode of water adsorption is a key step towards interpreting the performance of doped TiO2 materials as photocatalysts in aqueous media.

Generally speaking, increased water dissociation activity at TiO2 surface gives rise to higher photocatalytic performance in many aqueous target applications, such as water decontamination, owing to the increased presence of photogenerated radicals [START_REF] Henderson | Structural Sensitivity in the Dissociation of Water on TiO2 Single-Crystal Surfaces[END_REF][START_REF] Schaub | Oxygen Vacancies as Active Sites for Water Dissociation on Rutile TiO2(110)[END_REF]. Favourable dissociation energetics of water adsorbed at the different surfaces of TiO2 are reported to arise as the result of oxygen vacancies, structural defects and the proximity of acidic and basic sites. For this reason, the effect of localised dopants and electronic interactions on the dissociation energetics of surface adsorbed water is of interest towards interpreting dopant effects on photocatalytic performance.

The aim of the present work is to disentangle multiple physical phenomena and shed new light on the effects of copper doping in titanium dioxide photocatalysts by considering multiple aspects of surface interactions from an energetics perspective. This is studied by evaluating the stability of copper at different surface sites in anatase TiO2 including the interaction of surface chemistry and dopant speciation. Through this Density Functional Theory (DFT) based study we assess the mechanisms through which the presence of Cu in TiO2 photocatalysts may give rise to enhanced performance and the circumstances in which this enhancement is anticipated.

Methodology

Photocatalysis is a surface mediated phenomenon, and therefore in computational studies towards such applications it is most appropriate to focus on electronic interactions localised at surface regions rather than bulk behaviour, which may differ fundamentally. Furthermore, by focusing on a terminated surface, application-relevant behaviour of titanium dioxide photocatalysts can be computationally studied by including adsorbate interactions in simulations. In the present work we focus our study on the (101) surface plane of anatase phase TiO2 (a-TiO2).

The metastable anatase phase is typically the first crystalline phase formed through most synthesis procedures and is the most frequently studied phase in photocatalysis [START_REF] Hanaor | Sand Supported Mixed-Phase TiO2 Photocatalysts for Water Decontamination Applications[END_REF][START_REF] Shannon | Kinetics of the Anatase-Rutile Transformation[END_REF]. The (101) surface is chosen as this family of crystallographic planes is the most thermodynamically stable and therefore the most appropriate for energetics based computational studies. It also represents the majority of the surface area formed in commonly synthesised materials [START_REF] Gong | Steps on anatase TiO2(101)[END_REF][START_REF] Hebenstreit | Scanning tunneling microscopy investigation of the TiO2 anatase (101) surface[END_REF].

As illustrated in Fig. 1, the anatase (101) surface was constructed by stacking three a-TiO2 layers with vacuum space of 20 Å added normal to the (101) surface separating consecutive slabs. Water molecules were adsorbed on one side of the slab only while the ions on the outermost layers of the opposite surface were fixed to their bulk positions during the geometry optimisation. In the next step, a 1a×4b surface supercell of dimensions 10.90 Å × 15.10 Å was constructed exposing eight outermost O atoms on the surface. Density functional calculations were carried out within augmented plane-wave potential [START_REF] Blochl | Projector augmented-wave method[END_REF][START_REF] Kresse | From ultrasoft pseudopotentials to the projector augmentedwave method[END_REF] formalism as implemented in VASP code [START_REF] Kresse | Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[END_REF][START_REF] Kresse | Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set[END_REF]. Brillouin zone sampling was carried out by choosing a 2×2×1 k-points set within a Monkhorst-Pack scheme that generated a grid with spacing of ~0.05 Å -1 between k points while the energy cut-off was set to be 500 eV. Total energy convergence test was performed by increasing the k-point mesh with ~0.03 Å -1 spacing; it was found that the total energy differs only by 10 -6 eV/atom. Additionally, we recalculated the adsorption energy of few configurations of water molecule on the surface in the supercells with stacking of four layers of a-TiO2. We found that the adsorption energy differed by only ~0.1 meV. Therefore, the results were well converged with respect to k-point mesh and supercell thickness. For exchange-correlation functional, we used generalised gradient approximations (GGA) as parameterised by Perdew and Wang [START_REF] Perdew | Generalized Gradient Approximation Made Simple[END_REF]. Furthermore, in order to assess the magnitude of the dispersion interaction on the adsorption energies, we also repeated the calculations using the non-local van der Waals (vdW) correlation functional that approximately accounts for dispersion interactions as proposed by Dion [START_REF] Dion | Van der Waals Density Functional for General Geometries[END_REF] and implemented by Klimeš et al. [START_REF] Klimes | Van der Waals density functionals applied to solids[END_REF] and Roman-Perez et al. [START_REF] Roman-Perez | Efficient Implementation of a van der Waals Density Functional: Application to Double-Wall Carbon Nanotubes[END_REF]. Results of both GGA and vdW functionals are presented in this work.

Results

Water on Pristine a-TiO2 (101) 3.1.1. Associative Water Adsorption

In order to find the most stable configuration of the intact water molecule on the TiO2 anatase (101) surface, we examined all possible configurations in which a water molecule could be positioned at different Ti or O surface sites while simultaneously accounting for all possible orientations of the water molecule with respect to the O-Ti-O bonds of the surface. As presented in Fig. 2, all considered configurations relaxed to three distinct configurations labelled A1-A3. In configuration A1, the water molecule's O atom is located near the Ti5c site. In configuration A2, the water molecule's O atom is still located near the Ti5c site however with a different orientation. In the case of configuration A3, the water molecule's O atom is located near the Ti6c site. In this case the water molecule was only stable in the presented orientation. The water molecule was not found to bind to an O site. The adsorption energy (E a ) is defined as follows:

E a = -[Econf-Esurface-Ewater],
where Econf is the total energy of the surface and the water molecule for a given configuration, Esurface is the total energy of the surface and Ewater is the total energy of the water molecule. Positive E a values indicate attractive interaction between the water molecule and the surface. The corresponding adsorption energy of each configuration is given in Table 1. Configuration A1 was found to be the most stable configuration on the TiO2 surface with E a of 0.87 eV within the GGA framework. In this configuration the distance between water molecule's O atom and the closest Ti atom from the surface (d1) was 2.24 Å. The calculated E a and d1 of configuration A1 is in good agreement with the previously reported values of 0.82 eV and 2.27 Å for the same configuration [START_REF] Aschauer | Ab initio simulations of the structure of thin water layers on defective anatase TiO2(101) surfaces[END_REF]. As the distance between the O atom and the closest Ti site (d1) increased in A2 and A3 configurations, the adsorption energy decreased to 0.57 eV and 0.10 eV respectively. When the van der Waals interaction was considered, the adsorption energies increased by a considerable margin; E a for A1, A2 and A3 configurations were found to be 1.16 eV, 0. 81 eV and 0.23 eV respectively. Nonetheless, the trend of the stability was the same as that of the conventional GGA calculations. The distance between water molecule's O atom the closest Ti atom, however, did not change drastically in the optimised configurations within the framework of vdW interaction.

Configura tion

GGA vdW

E a (e V) d1 (Å ) d2 (Å ) E a (e V) d1 (Å ) d2 (Å ) A1 0.8 7
2.2 4

1.9 9

1.1 6

Dissociative Water Adsorption

In Configurations B1-B3 are presented in Fig. 3 while the dissociation energies are presented in Table 2. Configuration B1 represents the closest possible distance between the OH group and the disassociated H atom with r = 1.95 Å when optimised in GGA scheme.

In this case, as indicated in the isolated surface hydrogen is located on the top of a nearby O3c site with E d of -0.75 eV. In configuration B2, the isolated hydrogen is located slightly further at a distance of 2.11 Å on the top of an O2c site with an E d of -0.30 eV.

In configuration B3, the isolated H was located at a distance of 4.34 Å on the top of an O3c with an E d of -0.81 eV. When vdW interaction was included, the dissociation energies all slightly decreased nonetheless still preserving the trend obtained by the GGA. The change in the optimised structures was even more subtle. Since in all cases the E d was negative, the dissociation of water molecule on the a-TiO2 (101) surface is not thermodynamically favoured. In this regard, undoped (101) surfaces act contrarily to (001) surfaces at which the water molecules are reportedly adsorbed dissociatively [START_REF] Gong | Reactivity of Anatase Nanoparticles: The role of the minority (001) surface[END_REF][START_REF] Vittadini | Strucutre and energetics of water adsorbed at TiO2 anatase (101) and (001) surfaces[END_REF].

Water adsorption on Cu doped a-TiO2 (101) 3.2.1. Cu on TiO2 Surface

We first identified the most stable substitution site for the Cu atom on the outermost layer of the a-TiO2 (101) surface by comparing the total energies of the configuration in which Cu atoms substitute for Ti5c [Fig. 4(a) and (b)] and the configuration in which Cu substitutes a Ti6c site [Fig. 4(c) and(d)]. Under GGA, Cu substituting for Ti5c was found to be 0.26 eV more stable than the case in which Cu substitutes Ti6c. This margin of stability increases to 0.39 eV in the case of vdW inclusive calculations. The density of states (DOS) of both pristine and Cu doped surfaces as calculated by GGA method are presented in Fig. 5(a) and (b) respectively. According to Fig. 5(a), the intrinsic bandgap in TiO2 surface layer is ~2 eV which is considerably smaller than the experimental value of ~3.1 eV. This underestimation is attributed to the GGA's inherent lack of charge derivative discontinuity [START_REF] Sham | Density-Functional Theory of the Energy Gap[END_REF]. Nonetheless, GGA's DOS analysis is still insightful for qualitative evaluation [START_REF] Mardirossian | Exploring the limit of accuracy for density functionals based on the generalized gradient approximation: Local, global hybrid, and range-separated hybrid functionals with and without dispersion corrections[END_REF]. As demonstrated in Fig. 5(b), the inclusion of Cu on the outermost layer results in an inter-bandgap states in the middle of the fundamental bandgap. This interbandgap peak would be expected to manifest optically as a reduced bandgap, and indeed an effective reduction of the bandgap by Cu doping has been previously observed experimentally [START_REF] López | Photophysical and photocatalytic properties of nanosized copper-doped titania sol-gel catalysts[END_REF][START_REF] Yoong | Development of copper-doped TiO2 photocatalyst for hydrogen production under visible light[END_REF].

Furthermore, charge population analysis reveals that there are 8.97 electrons in Cu's d orbitals indicating an oxidation state of 2+ which is in contrast to bulk Cu dopant behaviour [START_REF] Assadi | Theoretical study on copper's energetics and magnetism in TiO2 polymorphs[END_REF]. In order to investigate the possibility of Cu aggregation which is a prerequisite for formation of a secondary CuO, we constructed two configurations with two Cu atoms substituting Ti at the surface. In the first configuration the Cu atoms were located at the closest proximity of 3.07 Å from each other while in the second configuration the Cu atoms were located at the furthest distance possible within the supercell of 8.07 Å. We found that the configuration with Cu atoms farthest apart was ~2 meV more stable indicating the absence of a strong tendency towards aggregation among Cu atoms at the a-TiO2 surface.

Associative Water Adsorption

We examined the effect of Cu substitution on the water molecule's associative adsorption by calculating the adsorption energy of a water molecule near a Cu atom that substituted a Ti5c. From examining all possible configurations, it was found that, as with pristine surfaces, the A1 configuration is the most stable condition for water adsorption at Cu doped a-TiO2 (101) surface. In this case, E a was found to be 0.88 eV under GGA and 1.02 eV under vdW calculations. By comparing these values to the E a values of the A1 configuration in Table 1, we find that the effect of Cu on the adsorption energetics of intact water molecules is insignificant regardless of the computational scheme employed.

Dissociative Water Adsorption

The dissociative structure was found to be stable only when the distance of H and the OH group at the beginning of the geometry optimisation was at least 4.90 Å in a similar atomic arrangement to that of configuration B3. When the H atom is located at a closer distance to the OH group in which the initial geometries are similar to those of configurations B1 and B2, due to outward relaxation of the Cu atom in the vicinity of the water molecule, in the optimised geometry, the OH group and the isolated hydrogen atom bind together to form an intact water molecule. The relaxation pattern for the case in which the isolated H atom is located on the top of the O2c site at a distance of 2.75 Å to OH group's O atom is illustrated in Fig. 6. For true dissociative geometry in which the H atom was far enough at 4.90 Å, the dissociation energy was found to be -1.84 eV for the case of GGA and -2.00 eV for the case of vdW functionals. Therefore, the presence of substitutional Cu dopant is found to further inhibit water dissociation at Cu doped a-TiO2 (101) surface.

Effect of Carrier doping

In order to investigate the effect of photoinduced electron and hole on the adsorption energetics of water, we recalculated the adsorption energies and the dissociation energies in the presence of free carriers. We simulated the presence of a hole in the system by substituting an O atom with a N atom. Likewise, we simulated the presence of an electron in the system by substituting an O atom with a F atom. By using doping as a model for generating carriers, we avoided the large finite size effects that result from the uniform charge background. Furthermore, it has been shown previously that carriers generated by doping accumulate near the surface resembling the photo-generated electrons and holes [START_REF] Boonchun | Role of photoexcited electrons in hydrogen evolution from platinum cocatalysts loaded on anatase TiO2: a firstprinciples study[END_REF]. To calculate the E a , we used a configuration similar to A1 (most stable configuration for associative water adsorption) and replaced an O atom from the bottom layer with either N or F. Such a site for the carrier dopant eliminates any undesired geometrical effects on the surface. To calculate E d , on the other hand, we constructed a configuration similar to B2 (lowest energy configuration for dissociative water adsorption) with carrier dopants located at the bottom layer. For Cu doped systems, carrier doped structures were based on the most stable associative and dissociative structures. These calculations were performed with GGA functional only and the results are presented in Table 3. In the case of hole doping, the adsorption energy of water molecule on pristine surface remained the same at 0.87 eV while in the case of electron doping, it slightly increased to 0.88 eV. The dissociation energy on the other hand remained the same as that of the undoped system at -0.30 eV. For Cu doped surfaces, the adsorption energy for the hole doped system was 0.81 which is slightly lower than the 0.88 eV of the undoped system while for the electron doped system, the adsorption energy was slightly higher at 0.92 eV. The dissociation energy of the Cu doped surface also varied slightly with carrier doping: In the hole doped system, E d was -1.77 eV while in the electron doped system E d was -1.93 eV (for comparison E d in undoped system for Cu doped surface was -1.84 eV).

Discussion

The present study focuses on the physicochemical aspects of anatase surfaces in pristine and copper doped materials. In particular, we focused on interactions with adsorbed water at a surface unit representing the (101) family of planes, the most energetically favourable and widely present crystallographic surface in anatase materials [START_REF] Cheng | Hydroxide Ions at the Water/Anatase TiO2(101) Interface: Structure and Electronic States from First Principles Molecular Dynamics[END_REF]. This methodology is in contrast to most DFT based computational studies which invoke bulk material rather than surface lattice systems.

Results from both GGA and GGA+vdW functionals indicate that at pristine anatase (101) surfaces the presence of adsorbed water is energetically favourable in a molecular or associative type adsorption rather than dissociative, for all adsorption configurations. This trend is consistent with the reported molecular water adsorption from earlier experimental and computational studies [START_REF] Vittadini | Strucutre and energetics of water adsorbed at TiO2 anatase (101) and (001) surfaces[END_REF][START_REF] Herman | Experimental Investigation of the Interaction of Water and Methanol with Anatase-TiO2(101)[END_REF][START_REF] He | Local ordering and electronic signatures of submonolayer water on anatase TiO2(101)[END_REF]. This may suggest lower levels of hydroxyl radical formation at this crystallographic surface and an increased dominance of pathways mediated through adsorbed molecular species.

The presence of a copper dopant at anatase (101) surfaces is found to be most stable in a disperse configuration suggesting the formation of secondary CuO phases is energetically unfavourable. This does not preclude the formation of secondary phases in the bulk and furthermore synthesis dependant non-equilibrium behaviour is likely to occur owing to inhomogeneous dopant distribution arising during processing or crystallisation. The presence of a substitutional copper dopant, most stable at five-coordinated Ti sites, is not found to result in increased water dissociation activity relative to the pristine material.

Surface dispersed Cu species are predicted to be substitutionally present in a 2+ valence states. This behaviour of Cu in terms of valence and lattice distribution is supported by the experimental findings of Li et al. [START_REF] Li | Role of Surface/Interfacial Cu 2+ Sites in the Photocatalytic Activity of Coupled CuO-TiO2 Nanocomposites[END_REF] who concluded that metal to metal charge transfer in Ti-O-Cu complexes at TiO2 surfaces enhance photoactivity through charge carrier separation while CuO clusters serve as exciton recombination centres. Additionally, our simulation results imply that as has been suggested by experimental studies [START_REF] Xia | Structure and photocatalytic properties of copperdoped rutile TiO2 prepared by a lowtemperature process[END_REF][START_REF] Li | Role of Surface/Interfacial Cu 2+ Sites in the Photocatalytic Activity of Coupled CuO-TiO2 Nanocomposites[END_REF], the reduction Cu 2+ + e -→ Cu + may serve as a further mechanism through which the lifetime of surface holes may be extended . This has been supported previously by spin-resonance [START_REF] Chen | Effect of Transition Metal Ions on the TiO2-Assisted Photodegradation of Dyes under Visible Irradiation: A Probe for the Interfacial Electron Transfer Process and Reaction Mechanism[END_REF] and diffusive reflectance spectroscopic observations [START_REF] Hamadanian | Synthesis, characterization and effect of calcination temperature on phase transformation and photocatalytic activity of Cu, S-codoped TiO2 nanoparticles[END_REF]. Increased hole lifetime in the presence of adsorbed water may enhance photoactivity mediated through the reaction 2h + + H2O → ½O2 + 2H + .

The introduction of Cu dopants is predicted in the present work to give rise to significant inter-bandgap states, which can be interpreted experimentally as bandgap narrowing. This prediction is in consistency with existing experimental reports and suggests that copper doping may impart visible light activity in anatase photocatalysts, as suggested in previous reports [10,24][47,54]. From simulated carrier doping it was found that neither the presence of a hole nor an electron significantly alters the E a and E d values in pristine and copper doped materials suggesting photoexcitation does not impart an increased propensity towards water dissociation at anatase (101) surfaces.

Conclusions

We used comprehensive density functional theory based on both GGA and GGA+vdW functionals to study the adsorption and dissociation of water molecules at anatase (101) surfaces, both pristine and doped with a copper dopant. The major findings can be summarised as follows: a)

We found the most stable site of associative water adsorption on a-TiO2 (101) surface. The adsorption energy of water on this site was 0.87 eV within the GGA functional and 1.16 eV when vdW correction is applied. b)

Dissociative water adsorption was found to be less energetically favourable having a total energy at least ~0.30 eV higher than the most stable configuration of intact water molecule adsorption. c) Cu dopant at a-TiO2 (101) surfaces is most stable when substituting for the Ti5c site. Cu dopants do not notably alter the adsorption energy of associative water molecules and further inhibit water dissociation. d)

The presence of carriers either holes or electrons does not meaningfully affect the E a and E d values of water molecules on pristine or doped surfaces suggesting photoexcitation does not cause further water dissociation. e)

The presence of substitutional copper dopants result in inter-bandgap states, which impart visible-light photoactivity in anatase. f)

The calculations with GGA and GGA+vdW functionals render the same trends, although for adsorption energies tend to be higher and dissociation energies tend to be lower with vdW corrected functionals.

Copper doping is often reported to result in enhanced photocatalytic activity in anatase, the most stable facets of which are the (101) surface. This work suggests that beneficial effects of copper doping in an equilibrium state at anatase (101) surface are more likely to arise through electronic interactions mediated through mechanisms of charge transfer and effective bandgap narrowing, rather than through the modification of surface chemistry in adsorbed water. The existence of secondary copper-bearing phases can not be excluded, as many synthesised materials are not in absolute thermodynamic equilibrium and the role of these phases merits further theoretical investigations. The present work did not consider higher energy planes, such as anatase (001), which often exhibit higher photactivity. The effects of dopants at such surfaces may differ from those found here. However, since the synthesis techniques used to give rise to high levels of (001) planes typically yield non-equilibrium crystallisation and growth behaviour, thorough theoretical and experimental investigation is required to identify the role of Cu dopants on those surfaces.

Fig. 1 .

 1 Fig. 1. Top (a) and side (b) views of (101) anatase TiO2 are presented. There two distinct sites for each of Ti and O atoms on the outermost layer of the surface. In the case of O, O2c has a coordination number of 2 while O3c has a coordination number of 3. In the case of Ti, Ti5c has a coordination number 5 while Ti6c has a coordination number of 6.

Fig. 2 .

 2 Fig. 2. Top and side views of the associative adsorption of the water molecule that were found to be stable. (a) and (b) correspond to configurations A1, (c) and (d) correspond to configuration A2 and (e) and (f) correspond to configuration A3.

  order to study the dissociative water adsorption, we calculated the dissociation energy (E d ) of the water molecule based on the most stable associative configuration A1. The dissociation energy is defined as the difference between the total energy of the associative adsorption and the dissociative adsorption. Negative values for E d indicate that associative adsorption is more stable. The configurations of dissociative adsorption were constructed by splitting the water molecule into OH+H ionic fragments on the a-TiO2 (101) surface. To examine the stability of such dissociation, E d was calculated for three dissociative configurations (B1-B3) in which the distance between H and O atom in the OH group (r) was gradually increased by placing the H atom on the crystallographically distinct O sites at various distances from the OH group.

Fig. 3 .

 3 Fig. 3. Top and side views of adsorption of sites that were found to be stable for dissociative water molecule. (a) and (b) correspond to configurations B1, (c) and (d) correspond to configuration B2 and (e) and (f) correspond to configuration B3. The distance values presented in the top panels correspond to r.

Fig. 4 .Fig. 5 .

 45 Fig. 4. Top and side views of relaxed CuTi surface dopant. (a) and (b) correspond to the case where Cu substitutes a Ti5c and (c) and (d) to the case where Cu substitutes aTi6c.

Fig. 6 .

 6 Fig. 6. (a) and (b) are the top and side views of the initial and (c) and (d) are the top and side views of the optimised (final) structures of water adsorption on Cu doped a-TiO2 (101) surface. The upward relaxation of Cu atom moves the OH group closer to the isolated H atom that initially was at a distance of 2.75 Å. Consequently, in the optimised geometry the split OH+H complex relaxes into an intact water molecule.

  ) and the dissociation (E d ) energy of water molecule on a-TiO2 and Cu doped a-TiO2 in the present of additional hole and electron.

Table 1 . Adsorption energy (in eV) of associative water molecule adsorption on anatase TiO2 (101) surface. d1 is the distance of the O atom in the water molecule to the closest Ti atom on the surface while d2 is the shortest distance of water molecules H atom to the closest O atom of the surface.

 1

Table 2 . Dissociation energy (in eV) of dissociative water molecule adsorption on anatase TiO2 (101) surface. d1 is the distance between the O molecule in OH group to the closest Ti atom of the surface while r is the distance of the detached H atom to the O atom of the OH group.

 2

			GGA			vdW
	Configura tion	E d (eV	d1 (Å	r (Å	E d (eV	d1 (Å	r (Å
		)	)	)	)	)	)
	B1	-0. 75	1.8 7	1.8 9	-0. 82	1.8 6	1.9 5
	B2	-0. 30	1.8 7	2.1 1	-0. 31	1.8 7	2.1 5
	B3	-0. 81	1.8 1	4.3 4	-1. 05	1.8 1	4.4 2

Table 3 . The adsorption energy (E a

 3

Acknowledgements

The computational facility was provided by Australia's National Computational Infrastructure and Intersect Australia Limited.


Guillaume Brunier

Edward J Anthony

Nicolas Gratiot

Antoine Gardel

Exceptional rates and mechanisms of muddy shoreline retreat following mangrove removal

Probably the largest regular shoreline fluctuations on Earth occur along the 1500 km-long wave-exposed Guianas coast of South America between the mouths of the Amazon and Orinoco Rivers, the world's longest muddy coast. The Guianas coast is influenced by a succession of mud banks migrating northwestward from the Amazon. Migrating mud banks dissipate waves, partially weld onshore, and lead to coastal progradation, aided by large-scale colonization by mangroves, whereas mangrove-colonized areas between banks (inter-bank areas) are exposed to strong wave action and undergo erosion. On large tracts of this coast, urbanization and farming have led to fragmentation and removal of mangroves, resulting in aggravated shoreline retreat. To highlight this situation, we determined, in a setting where mangroves and backshore freshwater marshes have been converted into rice polders in French Guiana, shoreline change over 38 years from satellite images and aerial orthophotographs. We also conducted four field experiments between October 2013 and October 2014, comprising topographic and hydrodynamic measurements, to determine mechanisms of retreat. The polder showed persistent retreat, at peak rates of up to -200 m/yr, and no recovery over the 38-year period of monitored change. Notwithstanding high erosion rates, mangrove shorelines show strong resilience, with recovery characterized by massive accretion. Retreat of the polder results in a steep wave-reworked shoreface with a lowered capacity for bank welding onshore and mangrove establishment. Persistent polder erosion is accompanied by the formation of a sandy chenier that retreats landwards at rates largely exceeding those in inter-bank situations. These results show that anthropogenic mangrove removal can durably modify the morphodynamics of muddy shorefaces. This limits the capacity for shoreline recovery and mangrove reestablishment even when there is no sustained long-term deficit in mud supply, as in the case of the Amazon-influenced Guianas coast.

Introduction

Mangroves are inter-tropical coastal forests that develop on muddy shores. They contribute to coastal sedimentation by trapping sediment through their complex aerial root structure (e.g., Carlton, 1974;Alongi, 2008;Victor et al., 2006), and to coastal protection by dissipating waves and currents (Massel et al., 1999;Quartel et al., 2007;Gedan et al., 2011;Kazimi et al., 2018). Mangroves are a particularly important component of the 1500 km-long Guianas coast of South America between the mouths of the Amazon and Oronoco Rivers (Figure 1), where they play an active role in coastal advance by colonizing and stabilizing the inner parts of mud banks (Proisy et al., 2009;Anthony et al., 2010Anthony et al., , 2014;;Gensac et al., 2011;Toorman et al., 2018). Shoreline changes along the Guianas coast are controlled by the migration, towards the mouths of the Orinoco River, of large mud banks that transport a fraction of the mud (~20%) supplied by the Amazon (i.e. 750 to 800 × 10 6 tons/year, Martinez et al. (2009)). The overarching expressions of these shoreline changes are onshore welding of the inner part of the mud bank, its rapid colonization by mangroves, commonly over several tens of km 2 a year, bank consolidation (termed 'bank' phase), and equally rapid shoreline erosion ('inter-bank' phase) a few years later (Gardel and Gratiot, 2006) in sectors between banks exposed to strong wave action. Banks dissipate waves, aided by mangroves. By promoting wave-energy dissipation, mangroves contribute to welding of the inner parts of banks to the terrestrial shoreline (their 'land-building' role) and slow down the erosion process (their coastal protection role) until the next bank phase (Anthony and Gratiot, 2012). The ensuing spatially and temporally varying shoreline changes result from complex interactions between hydrodynamic, morphodynamic, rheological and biological processes (Proisy et al., 2009;Gensac et al., 2011;Anthony et al., 2014;Gratiot and Anthony, 2016). The extent to which the shore-welded part of a mud bank is preserved from erosion in the inter-bank area during the bank-migration process determines the degree of coastal progradation generated by each bank (Allison and Lee, 2004;Anthony et al., 2010Anthony et al., , 2014)). Each inter-bank phase results in the partial, or rarely, total removal, of the coastal stratigraphic package built during accretionary bank phases, signifying that there is a net coastal plain growth with each cycle (Allison and Lee, 2004). Progradation of the Guianas coast associated with mud-bank sedimentation aided by mangrove 'landbuilding' over the last 5-6000 years has generated a coastal plain several kilometres wide in places (Augustinus, 1978(Augustinus, , 2004;;Augustinus et al., 1989;Prost, 1989;Wong et al., 2009).

Figure 1

General overview maps of the Guianas coast showing regional setting and location of study site (a, b, c); close-up view of the polder and field survey site (d); aerial photograph showing polder plot undergoing erosion, comprising a muddy foreshore and an overlying sandy chenier (e); cross-section of typical stratigraphic units in Western French Guiana (from Prost, 1989) (f). ARD: Amazon River delta; ORD: Orinoco River delta; MBB: Mud-bank migration belt; FG: French Guiana; S: Suriname; G: Guyana; VN: Venezuela.

In Suriname and especially Guyana, large tracts of the muddy Holocene coastal plain built from mud supplied by the Amazon have been urbanized or converted to rice farms and, increasingly, shrimp farms, implying the emplacement of polders delimited by dykes and canals (Anthony and Gratiot, 2012;Anthony, 2016). Mangroves, and, in places, freshwater swamps that developed behind cheniers, have been removed to make place for cities, such as Georgetown in Guyana, urban expansion seaward as in Paramaribo in Suriname, and for rice fields and shrimp farms, as along large tracts of the coast of Guyana. This situation embodies a paradox as all these transformations result in recourse to protection against the sea by relatively costly engineering structures in lieu of the natural protection mangroves provide.

Once mangroves and freshwater swamps are removed, engineering structures emplaced to stabilize the shoreline alter wave dissipation and hinder muddy sedimentation, and this can result in aggravation of coastal retreat (Anthony and Gratiot, 2012;Winterwerp et al., 2013). However, the processes involved in the erosion of modified shorelines no longer protected by dykes have not been studied on these coasts. The aims of this manuscript are two-fold: (1) analyze rates of multi-decadal shoreline change for areas of mangrove, freshwater marshes formed behind cheniers, and polders where the original mangrove and marsh vegetation has been removed, (2) describe the mechanisms of substrate erosion in areas of mangrove removal (polders) on the basis of shorter-term (one year) field experiments. The study site was originally colonized by sea-front mangrove forests backed by brackish and freshwater marshes, and was reclaimed in the 1980s to develop rice cultivation in French Guiana, in the same way as the much more enterprising rice ventures all along the Suriname and Guyana coastal plains. Modifications of the muddy mangrove shoreline have been much less undertaken in French Guiana, a European Union territory, where mangrove forests come under the directives of wetland protection. We quantify rates of regular shoreline change that are exceptional at the world scale, and contribute here to a better knowledge of the erosional processes aggravated by empoldering on this dynamic muddy coast, and their temporal and spatial variability.

Study area and regional context

The study site is part of a 50 km-long empoldered portion of the French Guiana coastal plain between the mouths of the Organabo and Mana Rivers (Figure 1). It is currently affected by three mud banks that have been migrating alongshore over the last 38 years, with phases of coastal advance alternating with retreat and stability. These phases are presented in the results, and discussed thereafter. Mud-bank migration and the attendant coastal changes are mainly controlled by the offshore wave climate (Gratiot et al., 2007;Walcker et al., 2015), which is dependent on seasonal variations in trade winds and rainfall. The regional climate comprises a dry season with 30 to 150 mm of monthly rainfall from August to the end of November, and a rainy season with 300 to 500 mm the rest of the year. The latter season is characterized by peak waves in January with significant wave heights close to 2 m and peak periods of 9 s that decrease to dry-season values of 1.3 m and 7 s in July, with minimal wave heights of about 1 m prevailing in August (Gratiot et al., 2007). Tidal data provided by the French Service Hydrographique et Océanographique de la Marine (SHOM) show a semi-diurnal regime with a mesotidal spring-tide range of 3.5 m. Decadal-scale hydrodynamic changes along this coast have been shown to be largely related to the influence of the North Atlantic Oscillation on waves, which generate variations in the size and mobility of mud banks (Walcker et al., 2015).

The polders are part of a low composite Pleistocene and Holocene coastal plain 10 to 20 km wide (Figure 1) comprising Amazon mud and sandy/shelly cheniers. In French Guiana, the 'Old' (Pleistocene) coastal plain comprises large cheniers of coarse white sand with podzols overlying muddy deposits, and correspond to the Coswine unit in the local geological nomenclature (named the Coropina unit in Suriname). The 'Young' coastal plain is represented by Holocene-to-modern mud and narrow cheniers of finer sand, dominantly quartz in French Guiana but rich in shells in Guyana. The cheniers are separated by swales comprising fresh and brackish water marshes and mangrove forests, the latter acting especially as the seafront buffer during inter-bank erosion.

The French Guiana polder project, funded by the European Council and the French Government, was inspired by the Dutch model of rice production in neighbouring coastal Suriname. In the course of this operation, from the early 1980s to the 1990s, the mangrove vegetation, freshwater marshes, and underlying original acidic soils (mainly peat layers) were massively removed in order to flatten the land. 28 rows of polder plots 500 m-wide and 250 mlong in the alongshore and cross-shore directions were enclosed by mud dykes. The mean plot elevation was 1 m enclosed by 2 m-high dykes. Rice production was carried out for about 20 years up to the early 2000s before salinity intrusion in the canals, facilitated by inter-bank erosion, rendered these polders unsuitable for rice cultivation. The current polder shoreline exhibits the following erosion features (Figure 1): (1) an intertidal mud platform cut into an erosion embayment and bounded by erosional bluffs, (2) an overlying chenier encapsulated inside each plot by dykes and (3) the former cultivated polder in the backshore.

Methodology

Analysis of shoreline change Shoreline change was analysed from the interpretation of satellite images and aerial photographs covering 38 years (1976 to 2014). Six pictures of varying spatial resolution were compiled from various databases (Table 1): 30 m/pixel for Landsat 5 TM images, 20 m/pixel for SPOT 5 images, and 0.5 m/pixel for aerial photographs. We used the Universal Transverse Mercator (UTM) 22 North zone and World Geodetic System 1984 (WGS 84) ellipsoid for coordinate referencing. For each date, the shoreline position was defined as a vector line using GIS ArcGIS desktop® v10.2. The shoreline 'markers' in this muddy coastal context were defined, depending on image resolution, as the limit between the sea and the mangrove fringe, or brackish-water vegetation front and active cheniers in the empoldered area.

Shoreline change was estimated through a statistical analysis of a cross-shore change rate, the End Point Rate (EPR) method of the Digital Shoreline Analysis System v4.3 (DSAS, Thieler and Danforth, 1994) toolbox for ArcGIS desktop® v10.2. This method is commonly used in numerous coastal change studies (e.g., Acciarri et al., 2016;Jonah et al., 2016). Change rates, in metres per year, are calculated as the variation between two shorelines along cross-shore transects generated by DSAS (Figure 2), divided by the time lapse between two images in decimal years. We used a relatively close transect spacing of 200 m in order to obtain a highresolution view of coastal changes over the study period. The experiments were designed with the aim of gaining an understanding of the shortterm morphodynamics and evolution of the polder plot over a one-year period covering the seasonal wave-climate variability and a variety of tidal range situations. A preliminary scrutiny of the high-resolution orthophotographs indicated a relatively homogeneous pattern along the empoldered stretch of coast, which is characterized by a cell structure for each polder enclosed by cross-shore dykes. Consequently, we chose to study a polder located in the middle of the empoldered sector (Plot 10 from the East, Figure 1, map d). This plot also had the advantage of being easy to reach using a four-wheel drive vehicle at low tide.

Field monitoring consisted first in quantifying the morphological evolution of the plot from topographic surveys using a Real-Time-Kinematic Differential Global Positioning System (RTK-DGPS) Trimble R8 (Figure 3). We distinguished, over the plot, the chenier, which was monitored in continuous-acquisition mode, and the inter-tidal mud platform and its erosional features, which were surveyed based on point acquisition. The vertical uncertainty was estimated to be 3 cm. The survey data were referenced in UTM 22 North zone WGS 84 for planar coordinates and Earth Gravitational Model 1996 (EGM 96) geoid for elevation. From the topographic data, we created Digital Elevation Models (DEM) for each survey using ArcGIS desktop® v10.2. The method was based on Delaunay triangulation between points. The result was a Triangle Irregular Network (TIN) where a raster file was interpolated using the natural neighbour method. The DEM included the dykes and rice polder elevation as the onshore limits of the plot. We compared the DEMs in order to assess the sediment balance at the plot scale. For this, we compared the sediment volume above a plane, arbitrarily fixed at an elevation of -1 m for each DEM. Bedforms and erosional features were observed and measured during each survey.

Figure 3

Field survey methods: (a) example of a DEM produced from field surveys using RTK-DGPS (b). The cross-shore profile shown was used to determine the wave incidence θ from wave direction. Pressure sensors (c) were deployed along a cross-shore transect on the mud foreshore subject to wave attack.

Incident wave energy and dissipation were estimated in order to assess wave impacts on the inter-tidal platform and the chenier. To this end, we deployed, for three or four days each time, four to five NKE SP2T pressure sensors initially along one (October 2013, April 2014), and then three (July 2014, October 2014), equally-spaced cross-shore transects (Figure 3). The sensor locations were monitored during the RTK-DGPS surveys. The most offshore sensors were continuously in the subtidal zone while the others were exposed at low tide. The sampling frequency was fixed at 2 Hz (0.5 s) which is a commonly used frequency for gravity-wave monitoring in shallow waters. The pressure sensor accuracy is 0.02 m and wave heights and water levels under this value were neglected. For the wave-data analysis, we applied linear theory despite the nonlinearities that can be induced by shallow water. However, this approach is considered as a good first approximation (e.g., Paquier, 2014). Wave spectra were calculated over 20-minute bursts (2048 samples) using Fast Fourier transforms, and a 600 s Hanning window with 75% overlapping. The limit between gravity and infra-gravity wave domains was fixed at 0.05 Hz. For each burst, the mean water level (h) and the significant wave height (Hs) in metres, and the peak period (Tp), in seconds, were calculated.

Offshore wave climate conditions from October 2013 to October 2014 were determined from hindcast re-analysis data provided by the United States National Ocean and Atmospheric Agency (NOAA) using the Wave Watch III (WWIII) global model. We downloaded directions, significant wave heights and periods predicted for swell, wind-waves and the total sea-state wave climate. We also calculated the wave incidence angle, θ, relative to the polder plot shore from WWIII wave directions (Figure 4). We considered an incidence θ normal to the shore of (0°) using a cross-shore profile located in the centre of the plot. θ ranged from -90° (NW to NE quadrant) to 90° (NE to SE quadrant). The tidal levels during the surveys were downloaded from the predictive model of the French Navy Hydrographic office (SHOM) for Hattes beach (Maroni River estuary) near the study site.

38-year shoreline changes

The satellite images highlight the westward migration of three successive mud banks since the 1970s, namely from west to east, the Magnan, Organabo (MB1) and Iracoubo (MB2) banks. Migration speeds have been extremely variable over the nearly four decades covered by the images (Table 2). From the analysis of shoreline changes, the coastal dynamics of the study area can be considered under four main periods, each lasting approximately 10 years. The shoreline changes characterizing each of these periods are shown for the three coastal environments: mangroves, freshwater marshes, polders (Figure 4). The period 1976 to 1987 corresponded with the early phase of empoldering and was characterized by a large inter-bank zone in the west and an approaching mud bank (MB1) in the east. Inter-bank erosion of the mangrove-colonized shoreline fronting the polders and marshes (located a few kilometres inland at the time) was relatively moderate to severe, not exceeding -100 m/yr (Figure 4a). MB1 was accompanied by onshore welding (kilometre points (PK) 0-10), mangrove colonization and massive accretion exceeding 100 m/yr in places.

Between 1987 and 1999, erosion became generalized throughout the study site with maximum values of over -100 m/yr in alternating sectors of shore-exposed marsh (as a result of inter-bank mangrove removal) and mangroves. Erosion was moderate throughout the rest of the shoreline, protected by the westward migrating MB1 (Figure 4b). It is interesting to note that this generalized erosion, despite the passage of MB1, is akin to the persistence of inter-bank conditions. From 1999 to 2006, the pattern was more irregular alongshore, with massive progradation following mangrove colonization of mudflats associated with a new mud bank, MB2 between PK 5 and 15 (Figure 4c). In the inter-bank area between MB1 and MB2, erosion began to strongly impact the polders from the east with shoreline retreat rates of 150 to 200 m/yr. A large and continuous sandy chenier appeared following the erosion of old inland cheniers exposed to waves as the shoreline retreated. Erosion attained its maximum, over the 38 years of shoreline change monitoring, in the wave-exposed marshes and polder sector, during this phase, whereas progradation occurred further west (PK 40-45), favoured by MB1.

Between 2006 and 2014, the shoreline largely recovered, with progradation and mangrove colonization along much of the former marsh area, but erosion remained intense in the interbank area between MB1 and MB2, still exceeding -100 m/yr along several polder transects (Figure 4d).

Field observations of large-scale polder erosion

At the start of the field experiments in October 2013 the polder plot was in severe erosion. Three morphological units were observed in the field and are depicted in Figure 5:

a. an inter-tidal platform of highly bioturbated Holocene clay attacked by waves. This unit exhibited a concave profile or an erosion scarp in the sectors highly impacted by wave attack, with mud pebbles accumulating at the base of this scarp. Wherever exposed by erosion, the Holocene clay deposits were indurated to depths of 20 to 30 cm with traces of biofilms at the surface. The top of the platform comprised two layers: a 10 to 15 cmthick peat layer inherited from the old swamp, and a layer (≈ 50 cm) of soft mud corresponding to the soil of the former rice field. The platform was cut in the western part of the polder by a tidal channel bounded by a dyke that was being broken down by erosion; b. a sandy chenier overlying the platform and formed at the limits of swash runup at high tide. The chenier was 25 m wide and composed of medium to fine sand with a D50 of 170 µm (Créocéan, 2008). c. a polder backshore zone behind the chenier corresponding to the former rice field. This unit was subject to overwash by waves as the tide rose, and then submerged by tidal flow at high tide. The high-tide water flux created channels against the dykes. This area was colonized by sparse mangrove stands in places. The WWIII hindcast data highlight a typical seasonal wave climate over the period October 2013-October 2014 (Figure 6; Table 3): relatively high waves from October to July associated with the onset and strengthening of the trade winds and North Atlantic swell, and a dry season from July to October 2014 with lower waves. Figure 6 shows an example of in situresults from the pressure sensors, focused on a tidal cycle, and the relevant offshore WWIII hindcast data for the measurement period. The sensors located at the seaward edge of the mud platform showed relatively high Hs values that increased as the tide rose, thus highlighting a clear tidal modulation of incident waves. Hs over the platform showed a clear decrease compared to values measured at the seaward edge of the platform. From the results of these surveys, we deduced that during the beginning of the flood or at the end of the ebb, the seaward edge of the platform was affected by wave breaking, leading to continuous excavation of the substrate. During tidal submergence, the platform was flooded, and, depending on the water level and on platform morphology, the breaker zone moved from the seaward edge to the landward edge.

Collapsing waves propagated over this zone, and this could explain the high and variable Tp values (Figure 6). The chenier was essentially affected by runup and overwash, and occasionally flooded briefly during high water levels. The surface of the polder plot during the survey periods was subjected to intense erosion (Figure 7 and Table 4). Net surface and sediment losses of -70,000 m 2 and -177,000 m 3 respectively occurred over a period of 380 days. This represents an average rate of -183 m 2 and -466 m 3 per day. However, we noted a clear seasonal variability in erosion intensity.

This, and a detailed description of the evolution of the surface of the polder, are presented below. The polder showed a dissymmetric erosion of the inter-tidal platform and chenier retreat (Figure 6). In March 2014, large erosion embayments, up to 50 m wide, appeared in the eastern sector. The erosion scarps were up to 1 m high, and fresh incision marks indicated clearly that large blocks of the mud substrate were being cut and reworked by waves, resulting in the formation of mud pebbles that accumulated in the bottom of the embayment. The face of the scarp and the bioturbated mud layer showed alveolar breaking along an exposed dense network of small burrows (Figure 5), whereas the top of the scarp exhibited mud cracks created following exposure to the sun and heat. These cracks evolved into fractures extended by wave action, resulting in block falls. The peat layer was abraded by waves at its stratigraphic plane 5 m from the scarp. However, the thickness of the layer appeared relatively insensitive to wave action. The muddy former rice-field soils did not resist wave reworking. The chenier migrated over these soft deposits, which were exposed progressively as more dewatered and consolidated mud on the foreshore in the wake of chenier migration. The shape and rate of migration of this sand body were strongly conditioned by the erosion scarp. Landward migration in front of the eroded embayment and a tidal channel was more rapid than in the central part and, in these zones of faster migration, the chenier was flattened by overwash at high tide. The beach profile was globally reflective with a relatively steep beach face slope where the mud platform was wider, and a gentler more dissipative face where the platform was more severely eroded. To summarize, the surface and volume losses corresponded to average removal rates of -dissymmetry between the eastern and western part of the plot (Table 4).

As shown in Figure 7, at the end of the June-early July 2014 experiment, the erosion dynamic described above continued, but more intensively, following the widening of the erosion embayment in the east and deepening of the tidal channel in the west. The dyke in front of the channel and the backshore dyke were undermined by waves and progressively broken down.

The western part of the chenier began to migrate over the backshore dyke, while the eastern part became more flattened and subjected to more frequent overwash. Chenier retreat between March 2014 and June/July 2014 was less than during the previous period, with 20 m in the central part and 40 m in the eastern part of the polder. However, the erosion rate of the muddy platform exceeded that of the previous period with a retreat of 40 m in the central part and 60-70 m in the eastern part. We measured net surface and volume losses of -25,556 m 2 and -59,750 m 3 during this short period (Table 4): -15,830 m 2 and -34,510 m 3 for the eastern part and -9,726 m 2 and 25,240 m 3 for the western part of the plot. These values represent an average erosion rate of -260 m 2 /day and -610 m 3 /day over 98 days.

Erosion of the polder slowed down in October 2014, but was still significant (Figure 7). Both the platform and the chenier retreated by 20 and 40 m, respectively in the eastern and western sectors. The chenier appeared more flattened in its eastern part and generally more 'curly' in the centre. The western backshore dyke became completely breached, allowing the chenier to migrate towards the next plot inland. The surface changes and sediment balance over this period showed a net loss of -17390 m 2 and -43,940 m 3 , values that correspond to erosion rates of -150 m 2 /day and -379 m 3 /day over 116 days (Table 4). The dissymmetric platform erosion was still marked with surface and volume losses, respectively, of -9,594 m 2 and -27,825 m 3 for the eastern part and -7,796 m 2 and -13,115 m 3 for the western part. The hydrodynamic measurements showed the same conditions of wave dissipation as in the previous period. The deepening of the tidal channel in the backshore favoured further damage by waves at high tide of the longshore dyke enclosing the polder.

Discussion

Two aspects have been investigated in this study: (1) a comparison of shoreline change rates in a setting where three environments co-exist: mangroves, polders, and freshwater marshes, and

(2) the mechanisms and rates of muddy substrate retreat where the original mangrove and marsh vegetation has been removed to make way for polders. Close field monitoring of these mechanisms has also yielded information on chenier migration and on the plan-shape expression of inter-bank erosion embayments. The shoreline changes in French Guiana determined from satellite images and aerial photographs over 38 years throw light on the complex intermeshing of the impacts of anthropogenic mangrove removal with the larger-scale background mud-bank alongshore migration dynamics. The erosion rates observed in the course of the field experiments in 2013-2014 on the Mana polder are amongst the highest in the world on coasts subject to a seasonal 'normal' wave regime. These rates are not related to exceptional high-energy events such as storms or tsunami. They are inscribed in the long-term dynamics of alongshore-migrating mud banks between which erosion rates are commonly high (Anthony et al., 2014), but also reflect the intensification of erosion engendered by anthropogenic shoreline modification.

In the face of the inordinately large space-and time-varying shoreline advance and retreat associated with mud-bank migration, mangrove removal entails a loss of the buffering effect this vegetation has on wave energy (Massel et al., 1999;Mazda et al., 2002;Quartel et al., 2007) and in slowing down erosion during inter-bank phases. This, in turn, has led to the exacerbated coastal erosion monitored in the polder in French Guiana. Figure 4 highlights two important aspects: (1) notwithstanding high erosion rates associated with mangroves, shoreline sectors where mangroves had not been removed (PK 0-32; PK 42-59) showed strong resilience, with recovery leading to massive accretion; (2) the polder sector showed no resilience over the 38-year period of monitored shoreline change.

The polder sector (PK 32-42) and marshes showed the largest retreat rates (peak rates of 200 m/yr). The extreme retreat rates in freshwater marshes probably reflect the poor capacity of this environment, once exposed along the shore following mangrove erosion, to withstand erosion. The continued erosion of the polder sector throughout the period 1976-2014 (Figure 4) reflects a poor propensity for bank-induced shoreline recovery and regeneration. The first (1976)(1977)(1978)(1979)(1980)(1981)(1982)(1983)(1984)(1985)(1986)(1987) of the four phases depicted in Figure 4 corresponded to the predominance of an inter-bank phase that led to large-scale erosion (PK 18-59) at a time when the polders were still inland. Retreat was attenuated by the passage of mud bank 1 (1987)(1988)(1989)(1990)(1991)(1992)(1993)(1994)(1995)(1996)(1997)(1998)(1999), but the intertidal mudflats that developed in the wake of this bank were not sufficiently large to permit largescale mangrove colonization. Although wave dissipation was assured by the bank, thus mitigating erosion (Figure 4b), significant mangrove colonization may have been precluded because of insufficient intertidal accretion of the mudflat substrate, a key parameter in the success of mangrove establishment during bank phases (Proisy et al., 2009;Gensac et al., 2011). Once MB1 went past this sector, erosion of the polder and marshes ensued (1999)(2000)(2001)(2002)(2003)(2004)(2005)(2006), but much more intensely, to attain the peak rate of -200 m/yr (Figure 4c). This erosion was still prevalent between 2006 and 2014, associated with the inter-bank phase between MB1 and MB2 (Figure 4d). All other sectors of the coast associated with mangroves showed, over these four phases, a normal bank (accretion) and inter-bank (erosion) pattern.

The persistence of retreat in the polder sector seems to reflect the disruptive effect of empoldering on muddy accretion in the bank stage, replaced by abnormal erosive inter-bank conditions, and impairment of the capacity for rapid mangrove colonization. An important negative effect of empoldering is that of wave reflection from dykes which favours mud liquefaction, offshore mud transport and shoreline erosion, thus eventually leading to the failure of these dykes (Winterwerp et al., 2013;Toorman et al., 2018). These processes generate a steep and low, retreating shoreface associated with wave reflection (Figure 8a). In this context, the intertidal foreshore cannot accrete to a level enabling rapid and widespread of mangrove colonization (Proisy et al., 2009;Gensac et al., 2011), a process necessary for stabilizing mud and which strongly contributes to shoreline advance in the Guianas. Without mangrove contribution to sedimentation and wave energy dissipation, enhanced mud-bank liquefaction and alongshore mobility ensue, leading to an abnormal persistence of inter-bank conditions (Figure 8b). These conditions are also favourable to the segregation of sand from mud and formation of sandy cheniers (Augustinus, 1978;Anthony et al., 2010Anthony et al., , 2014)). Engineered shoreline modifications have been shown to impede mangrove seedling dispersal in Guyana (Anthony and Gratiot, 2012), but this is not likely to have played a significant role in the case of the French Guiana polders, given the relatively small area of polder establishment alongshore and the proximity of widespread older mangrove forests. Situations of aggravated erosion or low shoreline recovery have been reported from other coasts where mangroves have been removed (e.g., Mazda et al., 2002;van Wesenbeeck et al., 2015;Proisy et al., 2018). Unfortunately, these effects are not understood or considered in shoreline management perspectives in the Guianas. In Suriname, for instance, there is an entrenched belief in the virtues of dykes and seawalls that goes with a poor knowledge of the larger-scale shoreline processes and a misunderstanding of the role of mangroves in coastal protection. This situation is worsened by the belief that mangroves create an unhealthy environment (Nijbroek (2014). Similar observations have also come from other tropical field sites where the muddy coastline is engineered, such as in Thailand (Winterwerp et al., 2005), andVietnam (Albers andSchmitt, 2015).

'Natural' coastal dynamics unaltered by humans still prevails along large tracts of the coasts of Brazil, French Guiana, Suriname and Venezuela, unlike the highly human-modified Guyana coast. The variable but large spatial (multi-kilometric) and temporal (multi-decadal) scales of mud-bank dynamics are incompatible with rapid coastal modifications under the pressures of population growth, socio-economic development, and urbanization. This can lead to a whole spate of issues ranging from accelerated shoreline retreat to the necessity of rethinking coastal planning and management, including retreat strategies, shoreline protection, and mangrove replanting. This is especially the case within the overarching perspective of sea-level rise affecting these low coastal lands (Nijbroek, 2014;Anthony, 2016). The case of the Mana polder illustrates this very well because at the time of conversion into rice fields in the 1980s this area was simply considered as swamps and wet savannahs far from the sea. The mild buffering effect of mangroves associated with mud bank 1 probably clouded the perception of risk of coastal erosion in the inter-bank phase, a problem further exacerbated by the afore-mentioned strong spatial and temporal variability of bank-inter-bank morphology and phases (Figure 4).

In addition to contributing to a better understanding of impaired mangrove colonization, the results obtained from the one-year field survey have enabled us to establish the strong links and morphological feedback effects between erosion of the polder, the ensuing polder foreshore and shoreface characteristics, rapid shoreward chenier migration in the absence of mangroves, and peculiarities of the plan shape of the muddy shoreline undergoing erosion. Removal, during empoldering, of much of the peat from mangrove or freshwater swamp development lowered resistance to wave attack. Moreover, mangrove tree stumps and roots also constitute an efficient wave buffer that reduces erosion rates. Cheniers generally undergo more or less active landward migration over their mud substrate during inter-bank phases. This occurs by overwash as waves top the low-elevation beach and transfer sediments from the active beach face to the backbeach. This process can be slowed down considerably where the chenier migrates landward over mangrove trees (Anthony, 2016). Over the unvegetated polder, the chenier moved back freely and did not offer the same protective effect as on a natural coast. The bare mud layer was also more exposed to heat during low tide, which boosted mud cracking through intense evaporation. Landward chenier migration was strongly related to wave dissipation over the platform. The chenier retreated by overwash and this process was controlled by the distance between the breaking wave area at the scarp of the platform and the chenier seaward face.

Where the platform is large, the chenier face is located 70-80 m from the platform scarp and adopts a reflective profile. The chenier gradually migrates onshore through small overwash events during high tide, with sand being washed over from the berm to runnel, generating a coherent alongshore body (Figures 7,8). This dynamic allows reworking of fresh mud which is moved by waves as the tide rises (Figure 8). In natural sectors where the chenier migrates over an eroding mangrove fringe, the muddy surface is less exposed to mud cracks and to breakdown by waves.

The highest erosion rates observed at the scale of the plot occurred from the end of March to July 2014. WWIII simulations over this period showed that the offshore wave energy decreased compared to the October 2013-March 2014 period. We suppose that the erosion embayment created during the previous period enhanced the breakdown of the platform by waves. The tidal cycle also appears to play an important role. The rising tide leads to immersion of the muddy intertidal platform 2 h after the low tide peak. Wave breaking then becomes efficient on the overall structure over a time window of 6 h centred on the high-tide peak. This creates the concave morphology of the platform basement. Wave forcing on a seasonal basis leads to the formation of the large erosion embayments observed during the strong wave season, between October 2013 and March 2014 (Figure 8). Anthony et al. (2010) suggested that these erosion embayments, also commonly referred to as a 'happen coast' since they were thus first identified by Geijskes (1952), could be due to orbital wave-wave interactions such as those that generate megacusps on sandy shores. Apart from those reported by Geiskes (1952) and further documented by Augustinus (1978) on the Guianas coast, we are not aware of any reports in the literature of such marked erosion embayments on muddy coasts elsewhere. Following our field experiments reported here, we hypothesize that the appearance of erosion embayments in the eastern part of the plot reflects the influence of the main wave approach direction. The tradewind waves that dominate the coastal hydrodynamic regime between October and March come from the NE-E sectors and contributed actively to the formation of these embayments as a result of the relatively constant and regular angle of incidence and attack. The carving out of the embayments is most likely the expression of a combination of rheological factors, such as faulting at the top of the substrate due to mud cracks, and continuous alveolar dismantling at the scale of the numerous burrows (Figure 8). As reported in Fiot and Gratiot (2006), the formation of mud cracks following evaporation processes on intertidal mud mainly depends on the duration of emersion, which is controlled in turn by the tidal range and the elevation of the substrate. In our case, the duration of emersion appears to be high enough to enable thorough wetting and weakening of the surface of the mud deposits, preparing the terrain for wave reworking and breakdown into large blocks. This is illustrated in Figures 5 and8 where we observed fresh sub-vertical incisions along the first 20 cm of the scarp while the rest of the profile was more oblique relative to the substrate.

We did not examine the role of rainfall, but several authors (e.g., Mwamba and Torres, 2002;Ryu et al., 2004;Torres et al., 2003;Voulgaris and Meyers, 2004;Fiot and Gratiot, 2006) have shown that rainfall can play an important role in mudflat erosion or consolidation. Rain contributes to fluidization of the muddy surface. This is typical of the March to July period when heavy and sustained rainfalls occur in French Guiana.

Conclusions

This study has focused on the negative impact of polders on mangroves, and on their role in shoreline changes. The Guianas coast is strongly influenced by mud banks migrating northwestward from the Amazon. Shoreline changes are inscribed in bank (shoreline advance) and inter-bank phases (shoreline erosion). Over a 38-year period, erosion persisted along the polder shoreline, notwithstanding the alongshore passage of a mud bank, whereas adjacent sectors of coast where mangroves had not been removed showed resilience, following intensive inter-bank erosion, and remarkable accretion during bank phases. The lack of resilience along the polder shoreline reflects the disruptive effects of these artificial structures on normal mangrove colonization of shore-attached mud during bank stages. Polder dykes and seawalls favour the development and maintenance, in the course of shoreline retreat, of a steep, low reflective muddy shoreface and the persistence inter-bank conditions. A one-year field experiment highlighted the processes involved in the persistent erosion of the polder. Erosion was dissymmetric and more pronounced on the eastern part of the polder plot. This seemed to be related to the main incidence of offshore waves to the coast which came from the NE. The steep wave-reworked foreshore and shoreface formed following the persistent retreat of the muddy polder substrate entails a lower capacity for bank welding onshore and mangrove establishment. The reworking of the foreshore also favours the formation, in each polder compartment, of a sandy chenier. These cheniers freely and rapidly retreat landwards, under the influence of overwash processes, at rates that are largely exceeded compared to cheniers formed under natural inter-bank conditions. These results show that anthropogenic mangrove removal can lead to a durable modification of the morphodynamics of muddy shorefaces. This can, in turn, limit the capacity for shoreline recovery and mangrove re-establishment even when there is no sustained long-term deficit in mud supply, as in the case of the Amazon-influenced Guianas coast. At the regional scale, this work addresses a warning signal against large-scale removal, under the pressures of population growth, socio-economic development, and urbanization, of mangroves characterizing the muddy coastal plain deposits of the Guianas. The French Guiana example documented here highlights the need for more studies on the coastal bank and inter-bank dynamics.

Figure 2

 2 Figure 2 Illustration of shoreline change analysis using DSAS for ArcGIS Desktop 10.2. The shoreline change-rate analysis was complemented by a determination of the intertidal limits of mud banks on each image to assess mud-bank migration rates. Three mud banks were identified over the 60 km of study shoreline. Identification of mud banks from optical images is a rather delicate operation fraught with difficulties, but the authors have years of experience of work on these mud banks. Field surveys Four field experiments were conducted in October 2013, March 2014, July 2014, and October 2014. The experiments were designed with the aim of gaining an understanding of the shortterm morphodynamics and evolution of the polder plot over a one-year period covering the seasonal wave-climate variability and a variety of tidal range situations. A preliminary scrutiny of the high-resolution orthophotographs indicated a relatively homogeneous pattern along the

Figure 4

 4 Figure 4 Shoreline change analysis along 60 km of coastline over the period 1976 to 2014 and graphs of change rates (in m/yr) associated with mud banks (MB1, MB2) and inter-bank phases for four intervals: (a) 1976-1987; (b)1987-1999; (c) 1999-2006; (d) 2006-2014. Note the persistence of erosive 'inter-bank' conditions in the polder sector and the 'bank' recovery and massive advance of mangrove-colonized shoreline sectors.

Figure 5

 5 Figure 5 Overview of the surveyed polder on 25 th March 2014: (a) DEM; photographs: (b) erosion embayment with wave-reworked steep bluff and mud pebbles from bluff reworking; (c) closeup view of fresh and clear incisions at the top of the Demerara mud deposit (light grey mud layers). These deposits exhibit a peat layer 2 to 3 m in front of the bluff that is being progressively eroded at high tide; (d) washovers indicative of chenier onshore migration during high tide.

Figure 6

 6 Figure 6Offshore wave climate during the survey period (a), and topographic profile along transect of deployment of pressure sensors and in situ hydrodynamic parameters measured by the sensors during a tidal cycle on July 1, 2014 (b). Also added are the erosion rates in m 3 for each survey period.

Figure 7

 7 Figure 7Polder sectors (a1); wave climate parameters (WWIII) offshore of the polder during the survey period (a2); DEMS of the polder from successive surveys (a3-a6); and volume losses over the one-year survey (b). The eastern sector is more exposed to waves and has eroded faster.

Figure 8

 8 Figure 8 Schematic illustration of the observed erosion processes along a cross-shore profile in (a), and at the scale of the polder plot in (b). Persistent inter-bank conditions have prevailed in the polder sector where both mud-bank welding and mangrove colonization have been hindered by polder influence on the shoreface dynamics.

Table 1 .

 1 Satellite images and aerial photographs used in the

study Data source Date Resolution Archive

	Aerial photographs	17/08/1976	0.5 m	IGN
	Landsat 5 TM	23/07/1987	30 m	Earth Explorer (USGS)
	Landsat 5 TM	21/11/1999	30 m	Earth Explorer (USGS)
	Spot 4	26/11/1999	20 m	CCOG
	Spot 5	11/11/2006	10 m	CNRS French Guiana office
		05/08/2006
		30/08/2006
	Orthophotographs	01/11/2012	0.5 m	RNA
	Landsat 8	13/04/2014	30 m	Earth Explorer (USGS)

Table 2 .

 2 Mud-bank migration distances and rates in km/year for the period 1987 to 2014

	Migration distance along the coast (km)
		Magnan mud bank	Mud bank 1	Mud bank 2
			(MB1)	(MB2)
	1987-1999	4.35	20	18.7
	(12.32 years)
	1999-2006	Migrated across the mouth of the Maroni River onto	12.2	9.4
	(6.77 years)	Suriname
	2006-2014 (7.6 years)	Migrated across the mouth of the Maroni River onto	11	9.7
		Suriname
	Migration speed for each period (km/yr)
		Magnan mud bank	MB1	MB2
	1987-1999	0.352	1.622	1.516
	(12.32 years)
	1999-2006	Migrated across the mouth of the Maroni River onto	1.8	1.387
	(6,77 years)	Suriname
	2006-2014 (7,6 years)	Migrated across the mouth of the Maroni River onto	1.443	1.273
		Suriname

Table 3 .

 3 Average wave parameters: direction, significant height, peak period and incidence angle, for each field survey

		October 2013 -March	March -July	July -October
		2014	2014	2014
	Wave direction in degrees from	56.3	60.3	51.8
	North

Table 4 .

 4 Surface and volume losses for each survey period and for plot sectors from comparison of DEM

	Period	Overall surface	Daily surface	Overall volume	Daily volume
		loss (m 2 )	loss (m 2 )	loss (m 3 )	loss (m 3 )
	Eastern sector
	October 2013 -	-17,651	-106	-44,676	-269
	March 2014
	March 2014 -July	-15,830	-161	-34,509	-352.
	2014
	July 2014 -October	-9,594	-83	-27,826	-240
	2014
	October 2013 -	-43,075	-113	-107,010	-282
	October 2014
	Western sector
	October 2013 -	-9,062	-55	-28,638	-172
	March 2014
	March 2014 -July	-9,726	-99	-25,243	-258
	2014
	July 2014 -October	-7,796	-67	-16,114	-139
	2014
	October 2013 -	-26,584	-70	-69,995	-184
	October 2014
	Entire plot

Acknowledgements We acknowledge support from CEREGE UM 34 for the October 2013 experiment, and the CNRS Mission Interdisciplinaire and the Pépinière Interdisciplinaire de Guyane GUIASANDBEACH project for funding in 2014. Important funding was provided by the Belmont Forum-ANR Project 'BF-Deltas: Catalyzing Action Towards Sustainability of Deltaic Systems with an Integrated Modeling Framework for Risk Assessment'. Funding was

also provided by the ERDF OYAMAR project. Finally, we appreciate the operational support from the Amana Nature Reserve and the coastal team of the CNRS in French Guiana. Thanks also to the Western French Guiana Township Community Office (CCOG) for their support and for providing data from Créocéan. Salient suggestions for improvement were provided by two reviewers and by the Associate Editor.

• Acciarri A, Bisci C, Cantalamessa G, Di Pancrazio G. 2016