Anh T K Do

Aldo Sottolichio

Nicolas Huybrechts

Antoine Gardel

Circulation patterns and

Keywords:

come

Introduction

Located between 30°N and 30°S of latitude, tropical estuaries are frequently fringed by dense mangroves [START_REF] Anthony | Sediment dynamics and morphological stability of estuarine mangrove swamps in Sherbro Bay, West Africa[END_REF][START_REF] Bomer | Surface elevation and sedimentation dynamics in the Ganges-Brahmaputra tidal delta plain, Bangladesh: Evidence for mangrove adaptation to human-induced tidal amplification[END_REF][START_REF] Van Santen | Sedimentation in an estuarine mangrove system[END_REF][START_REF] Victor | Fine sediment trapping in two mangrovefringed estuaries exposed to contrasting land-use intensity, Palau, Micronesia[END_REF][START_REF] Willemsen | Sensitivity of the sediment trapping capacity of an estuarine mangrove forest[END_REF] or muddy coastal environment [START_REF] Anthony | The muddy tropical coast of West Africa from Sierra Leone to Guinea-Bissau: geological heritage, geomorphology and sediment dynamics[END_REF][START_REF] Chapman | Salt marshes and salt deserts of the world[END_REF][START_REF] Lugo | The ecology of mangroves[END_REF][START_REF] Wong | Asia-Pacific Symposium on Mangrove Ecosystems: Proceedings of the International Conference held at The Hong Kong University of Science & Technology[END_REF]. In contrast compared to temperate estuaries, the functioning of hydrosedimentary dynamics in tropical estuaries is less understood and studies are still sparse [START_REF] Kitheka | Coastal tidally-driven circulation and the role of water exchange in the linkage between tropical coastal ecosystems[END_REF][START_REF] Anthony | The influence of Amazon-derived mud banks on the morphology of sandy headland-bound beaches in Cayenne, French Guiana: a short-to long-term perspective[END_REF][START_REF] Capo | Morphology, hydrography and sediment dynamics in a mangrove estuary: the Konkoure Estuary, Guinea[END_REF][START_REF] Asp | Sediment dynamics of a tropical tide-dominated estuary: Turbidity maximum, mangroves and the role of the Amazon River sediment load[END_REF] as for instance for estuaries along the Guiana coastline in South America. The originality of these latter stands in the presence of fine sediment mostly originated from offshore supply whereas rivers rather bring coarse sandy material [START_REF] Jouanneau | Suspended matter and bottom deposits in the Mahury estuarine system (French Guiana): environmental consequences[END_REF]Pujos, 1987, Jounneau andPujos, 1988). It is the opposite configuration compared to many temperate estuaries where the muddy content comes from riverine contribution and the sandy material is located near the mouth as a result of inflow from the coastal area [START_REF] Fettweis | Seasonal, neap-spring and tidal variation of cohesive sediment concentration in the Scheldt Estuary, Belgium[END_REF][START_REF] Uncles | Observed fluxes of water, salt and suspended sediment in a partly mixed estuary[END_REF]. The Maroni is one of the largest estuaries along the Guiana coast in terms of width and river flow rate. However, few studies on its dynamics have been conducted, and they are mainly based on short-term data acquisition or geochemical evidence [START_REF] Berthois | Etude dynamique de la sédimentation dans trois cours d'eau de la Guyane française: la rivière Mahury, la rivière de Cayenne[END_REF]Hoorelbeck, 1968, Jounneau andPujos, 1988). Only recently, the Maroni and other neighbouring estuaries have spotted back the attention, as a significant demographic growth is expected, more especially along rivers and shoreline in French Guiana. One of the new observations of hydrodynamics was conducted by [START_REF] Ross | Intratidal and Subtidal Circulation in a Tropical Estuary during Wet Season: The Maroni, French Guiana[END_REF], which focused on a high river flow event to investigate subtidal circulation patterns. In terms of human impacts, the last dredging operation on the Maroni estuary occurred 25 years ago and to date no bridge or huge coastal structure have been built yet. It thus presents a rare chance to analyse circulation patterns and forcing mechanisms in a natural estuary [START_REF] Ross | Intratidal and Subtidal Circulation in a Tropical Estuary during Wet Season: The Maroni, French Guiana[END_REF]. For these different reasons, a deeper and updated description of the Maroni dynamics is thus needed in order to better anticipate changes related to the development of harbour activities and to the arrival of a coastal mud bank near the navigation channel [START_REF] Jolivet | Multi-decadal to short-term beach and shoreline mobility in a complex river-mouth environment affected by mud from the Amazon[END_REF]. With such a perspective in mind, different field surveys are conducted on the downstream part of the Maroni estuary during low and high river discharges. Since field data are still limited in space and duration due to difficult logistic conditions for field monitoring, a 3D hydrodynamic numerical model is also built to further explore different flow conditions. Different numerical models have already been developed to analyse the current and salinity on the Guiana continental shelf [START_REF] Chevalier | Modeling the influence of wind and rivers on current, salinity and temperature over the French Guiana continental shelf during the rainy season[END_REF][START_REF] Bourret | Tidal influence on the hydrodynamics of the French Guiana continental shelf[END_REF] or the turbid plume around mud banks [START_REF] Chevalier | Numerical analysis of the combined action of littoral current, tide and waves on the suspended mud transport and on turbid plumes around French Guiana mudbanks[END_REF]. Based on finite difference techniques, these previous models focus on the coastal dynamics along French Guiana coast but they were not used to analyse estuarine dynamics because of the lack of validation data and the poor mesh description inside the rivers. Even if this study focus on the particular case of the Maroni, results serve to lighten the estuarine dynamic of Guiana estuaries or more generally of estuaries influenced by a sediment source from adjacent sea area [START_REF] Xiao | Suspended sediment dynamics in a well-mixed estuary: The role of high suspended sediment concentration (SSC) from the adjacent sea area[END_REF][START_REF] Shimozono | Large-scale Channel Migration in the sittang River estuary[END_REF][START_REF] Wright | Dispersal and deposition of river sediments in coastal seas: models from Asia and the tropics[END_REF]. To reach these aims, first, collected in situ data are described for different flow rates and tidal amplitudes. This allows us to identify the length of salinity intrusion and to highlight the variation of velocity strength and concentration level inside the downstream estuary. Then, numerical results are exploited: (1) to investigate the interactions between stratification, circulation and residual current; (2) to provide insight about driving processes of the circulation; and (3) to deduce implication for sediment transport inside the central part of the estuary.

Regional context

Located at the border between Suriname and French Guiana, the Maroni estuary (Fig. 1) ends up inside the Amazonian mud banks system [START_REF] Anthony | The Amazon-influenced muddy coast of South America: A review of mud-bank-shoreline interactions[END_REF]. These coastal mud banks come from the part of the Amazonian turbid plume which is northwest transported by the Guiana oceanic current [START_REF] Wells | Physical processes and fine-grained sediment dynamics, coast of Surinam, South America[END_REF]. Once the turbid suspension reaches the Guiana shelf, it is transformed into individual mud banks [START_REF] Allison | Origin of Amazon mudbanks along the northeastern coast of South America[END_REF]. Between the Amazon and the Orinoco (Venezuela) rivers, mud banks are generally about 15-20 spaced out 15-25 km apart. Areas between mud banks called inter-bank areas are exposed to strong waves and undergo erosion. The mud banks migrate from 1 to 5 km/yr [START_REF] Gardel | A satellite image-based method for estimating rates of Mud Bank Migration, French Guiana, South America[END_REF], and they can attain 5 m thick, 10 to 60 km long, and 20 to 30 km wide [START_REF] Allison | Origin of Amazon mudbanks along the northeastern coast of South America[END_REF][START_REF] Froidefond | Migration of mud banks and changing coastline in French Guiana[END_REF]. During their shoreline migration along the French Guiana, Suriname and Guyana, these mud banks cross seventeen estuarine systems whose bottoms are mainly composed of sand or coarse sand in their central and upstream part. However muddy sediments are patchy observed in the downstream part. As suggested by previous studies [START_REF] Jouanneau | Suspended matter and bottom deposits in the Mahury estuarine system (French Guiana): environmental consequences[END_REF][START_REF] Jounneau | Suspended matter and bottom deposits in the Maroni estuarine system (French Guiana)[END_REF][START_REF] Orseau | Hydro-sedimentary processes of a shallow tropical estuary under Amazon influence. The Mahury Estuary, French Guiana[END_REF], the mud bank presence at an estuary mouth constitutes a source of fine sediment that may enter these estuaries.

Study site

The Maroni river is 677 km long with a watershed of 60,930 km 2 . In the estuarine area, its width is 700-900 m near Apatou, 100 km upstream from the mouth (KP100, Kilometric point, Fig. 1) and up to 4000-5000 m between KP7 to KP15. Small tributaries mostly on the right bank are flowing to the estuary and some islands built from alluvial deposits are present upstream Crique Vache (Fig. 1). The climate is equatorial and within the intertropical convergence zone. Well contrasted seasonal variations are characterized by a high river discharge season from late December to July, and a low river discharge season from August to December. Trade-winds are weak and characterized by a quasi-constant direction of about 10°-15° (direction from the north) throughout the year [START_REF] Gratiot | Trade-wind waves and mud dynamics on the French Guiana coast, South America: input from ERA-40 wave data and field investigations[END_REF]. Water discharge is estimated by Direction de l'Equipement, de l'Aménagement et du logement (DEAL) at Apatou via a rating curve. The mean annual discharge is reaching 1700 m 3 /s, with lower values down to 100 m 3 /s, during the low flow periods and higher values up to 5000 m 3 /s during the high flow periods. Bed material samples have been collected by [START_REF] Jounneau | Suspended matter and bottom deposits in the Maroni estuarine system (French Guiana)[END_REF] during low (November 1984) and high (May 1985) river discharge periods. Grain-size analysis, showed that the upstream part of the estuary (upstream of St Laurent) is composed of coarse sand (mean diameter 1-2 mm) whereas fine materials are found near the mouth.

The tide propagates up to 100 km upstream from the mouth, until a natural weir at Apatou. No continuous tidal gauge is installed inside the Maroni estuary even though water levels are recorded at three locations by the Port Authorities during two months each year.

Based on a T_Tide analysis [START_REF] Pawlowicz | Classical tidal harmonic analysis including error estimates in MATLAB using T_TIDE[END_REF], [START_REF] Sottolichio | Premières observations de la dynamique hydro-sédimentaire de l'estuaire du Maroni (Guyane)[END_REF] pointed out a small amplification from the mouth to Crique Vache (4 cm) and then a decrease of the tidal amplitude down to 10 cm until Saint Laurent du Maroni (KP35, SLM). The amplification is probably induced by the section reduction whereas the decrease can be due to the presence of island and a modification of the bed texture [START_REF] Sottolichio | Premières observations de la dynamique hydro-sédimentaire de l'estuaire du Maroni (Guyane)[END_REF].

Besides bed samples collection, [START_REF] Jounneau | Suspended matter and bottom deposits in the Maroni estuarine system (French Guiana)[END_REF] also identified the position of the salinity intrusion and the turbidity maximum during low and high discharge seasons by collecting water samples and suspended matter near the surface. During low hydrological conditions, the salt intrusion (S 0.5 isohaline) reached the first islands of the estuary (approximately KP 19), while under the high river flow conditions it stayed near the mouth (around KP 5). As for the turbidity maximum, during the low hydrological condition it had suspensed sediment concentration of up to 0.9 kg/m 3 in surface water, and was located in the lower estuary (downstream of the Coswine tributary, KP 9, Fig. 1) whereas, during the high river flow event, it was less extended, less concentrated (0.3 kg/m 3 ) and only appeared near the mouth (KP 2 to KP 3). Tidal variation inside the estuary is described by [START_REF] Berthois | Etude dynamique de la sédimentation dans trois cours d'eau de la Guyane française: la rivière Mahury, la rivière de Cayenne[END_REF]through shipboard profiles at different locations. During the survey of [START_REF] Berthois | Etude dynamique de la sédimentation dans trois cours d'eau de la Guyane française: la rivière Mahury, la rivière de Cayenne[END_REF], the measured flowrate is within 1800-2000 m 3 /s, close to the mean annual discharge. The main results from their study are shortly reminded here. The mouth (KP 2, Fig. 1) already corresponds to the limit of the oceanic influence. The salinity reaches 0.2-0.5 g/kg at low tide. The bottom peak velocity has more or less the same magnitude (0.4 m/s) during the flood and ebb. Periods of low velocity near the bottom are observed both during ebb and flood. In the central part (KP 15, Fig. 1), low salinity and sediment concentrations are observed. No fine sediment is available at the bottom and the turbidity level corresponds to advection from upstream. At high tide, the slack is well pronounced and even reaches the whole water column. It however happens in a very short period. Upstream the first islands (KP 28), ebb advection dominates during 7 h. Only 2 to 4 h is available for flood. Up to now, the knowledge about sediment dynamics in Maroni estuary is based on the works of [START_REF] Berthois | Etude dynamique de la sédimentation dans trois cours d'eau de la Guyane française: la rivière Mahury, la rivière de Cayenne[END_REF] and [START_REF] Jounneau | Suspended matter and bottom deposits in the Maroni estuarine system (French Guiana)[END_REF]. Since these two previous studies, although there is no scientific evidence, the estuary may have undergone morphodynamic evolution. It is thus necessary to update the knowledge about the circulation and the sediment transport and also to provide more details about intratidal variability (neap-spring) under a larger range of hydrological conditions. Gardel et al., this issue describe a development pattern wherein the Maroni estuary has tended to evolve towards a delta built from both Maroni river bedload and marine mud from Amazon river located approximately 750 km to the southwest. 1). During the fourth survey (EH4), the three station S2, S3 and S5 were sampled simultaneously. For each shipboard survey, data are collected every 30 min during a semidiurnal tidal cycle (12 h 30 min): salinity using CTD (CastAway © SonTek), velocity and flow direction using a single point current meter (Aquadopp © Nortek) and turbidity using an optical (OBS 5+ © Campbell Scientific) probe. The CTD sampling frequency is 5 s -1 . For the Aquadopp, the sampling frequency is 1 s -1 . The vertical profiles are collected by moving the sensor through the water depth since the sensor is punctual with only one cell. For the OBS 5+, the frequency is 1 s with an averaging period of 10 s. The OBS5+ measurement is based on the measurement of two optical signals: near and far field.

Methodology

The combination of the two signals allows to avoid saturation and thus to cover a wider range of sediment concentration than a classical OBS. Turbidity signal is converted into suspended sediment concentration (kg/m 3 ) using a calibration curve built in the lab with mud material collected in the field.

The calibration in the lab allows to cover a range of concentration levels up to 10 kg/m 3 . It should be kept in mind that the calibration is performed with only mud concentration whereas the sensor measures in the field organic and inorganic matters. An in-situ calibration would be probably more accurate but it requires a more complicated logistic to rapidly treat the water samples.

In addition, for EH3 and EH4 surveys, along-channel transects are conducted to locate salinity intrusion during low and high tide conditions using the moving vessel method [START_REF] Savenije | Salt intrusion model for high-water slack, low-water slack, and mean tide on spread sheet[END_REF]. Stratification strength is estimated using the stratification number "Sn" defined as the difference between bottom and surface salinity divided by depth averaged salinity. According to [START_REF] Hansen | New dimensions in estuary classification 1[END_REF], Sn higher than 0.1 corresponds to stratified estuary whereas values higher than 1 represent estuary with salt wedge. Besides, bathymetric surveys (Fig. 1) are performed using bi-frequency sonar sensor (Midas Surveyor 210/33 kHz © Valeport) during the low river discharge survey of 2016 and 2017, in the downstream part of the estuary. The mud thickness is estimated as the vertical distance between the two signals in low and high frequency. The recorded depth is corrected from tidal elevation using three tidal stations located along the survey area.

Numerical model

In this work, a 3D numerical model is built [START_REF] Do | Modeling and Quantification of Patterns of Salinity, Mixing and Subtidal Flow in the Maroni Estuary[END_REF] using the open source TELEMAC-MASCARET modelling system. TELEMAC-3D solves three-dimensional flow equations (Navier-Stokes) and transport-diffusion equations of passive tracer. The discretization in TELEMAC-3D [START_REF] Hervouet | Hydrodynamics of free surface flows: modelling with the finite element method[END_REF] is based on finite element techniques and unstructured mesh well adapted to describe real river geometry with isles, tributaries. For the turbulence, a mixing length model is selected and combined with [START_REF] Lehfeldt | Algebraic Turbulence Model for Stratified Tidal Flows[END_REF] damping functions. The computational domain extends into 90 km in width and 97 km in length for the coastal part. Inland, the domain extends until the limit of tide propagation, where measured river discharge is available. The distance between nodes of the horizontal mesh resolution decreases from 2.5 km in the coastal zone to 120 m inside the central part of the estuary, to 50 m in the tributaries and down to about 10 m around islands. The horizontal grid contains 19,694 nodes, 34,241 triangular elements. For the 3D mesh, 8 vertical planes are used with a finer resolution near the bottom. The distribution of vertical mesh layers from bottom to water surface have been defined as a percentage of the water depth as follows (0; 0.075; 0.15; 0.3; 0.5; 0.7; 0.85; and 1.0).

The computational domain contains three open boundaries. Upstream for Maroni and Mana rivers, daily river discharges are forced. Offshore, tidal level and currents are imposed using atlases of the Amazon shelf from Oregon State University. The offshore imposed salinity is 35 g/kg. A time step of 20 s is used for each case investigated. Most complete surveys are selected (EH3 and EH4) for calibration (Table 1) whereas the two others (EH1 and EH2) are used for verification. TELEMAC allows to use different friction formulations and associated friction coefficients as Chezy, Manning, Strickler or Nikuradse. The friction coefficient is then converted inside the code into a no-dimensional quadratic friction coefficient. The Strickler relationship has been selected using a spatial varying friction coefficient. The Strickler's coefficient, K (m/s) is in fact the inverse value of the Manning's coefficient. Three zones of constant Manning-Strickler coefficient are defined as coastal zone (with a depth larger than 20 m), central part of the estuary (limit from St Laurent to the area with depth less than or equal 20 m) and upstream islands (upstream part of St Laurent). The Manning-Strickler friction coefficient varies from 45 (m/s) in the coastal zone, decreasing to 35 (m/s) in the estuary and to 30 (m/s) in the upstream rive part.

Model performance is quantified through root mean square error (RMSE), and predictive skill (SS) introduced by [START_REF] Willmott | On the validation of models[END_REF]. RMSE and SS are summed up in Table 2 for the calibration (EH3) and Table 3 for the verification steps (EH1). Two cases, with full data sets including water levels, velocities and salinity have been selected here. EH3) indicates a very good agreement with a high skill coefficient, larger than 0.74. The average RMSE of velocity is very small (0.1 m/s) in the calibration case. In case of verification under low river discharge, EH1, the model skill for velocity at S3 also displays a very good agreement in both surface and bottom layer with a skill of 0.83 and 0.82, respectively. An exception is however observed for the skill value of bottom velocity at station S2 for the lowest discharge (EH1) with a little underestimation.

The model reproduces the seasonal variation in salinity intrusion between the low and high discharge.

Salinity is observed until upstream part (KP 32) during very low discharge, EH1 while the salinity is only observed at river mouth (station S4, KP 6) for high discharge, EH3, thus skill of salinity of station S2 and S3 are nearly zero in this case (Table 2). The model skill of salinity is slightly lower than for velocities and water level except the skill coefficient of bottom velocity at station S2. However, the main hydrodynamic patterns (velocity and salinity) are well reproduced by the model for both low and high discharges.

Results

Observed intra-tidal and neap-spring dynamics during high river discharge

Both field surveys during high river discharges are characterized by similar value (3600 m/s) though tidal range is changing from spring to neap tide. Intra-tidal variation of measured variables is illustrated on Fig. 2 where low water slack (LWS) is selected as "zero" for the time scale to facilitate the comparison between stations and season.

During neap tides, the tidal currents outline stronger peaks in velocity during the ebb, reaching a maximum of 1 m/s at station S2 (Fig. 2a), 0.94 m/s at S3 (Fig. 2c) and 1.17 m/s at station S4 (Fig. 2e). Salinity is only noticed near the river mouth at station S4 during high tide. The salinity reaches its maximum value of 8 g/kg at the bottom during high water slack (HWS, Fig. 2f) then it rapidly decreases down to almost null value during ebb and low water slack. The vertical salinity distribution at station S4 displays a strong difference between the bottom and the surface during flood. At stations S3 and S2, salinity is lower than 0.05 g/kg for both spring and neap tides (not shown in Fig. 2).

A phase difference between current speed and water level is observed i.e., 0.54 h after low water level at station S4, 0.67 h at station S3 and 1.75 h at station S2. Durations of low water slack (LWS) increase from the river mouth (0.54 h at S4) to the upstream part since river discharge at the upper estuary gains influence. At station S2, durations of HWS and LWS are estimated as 0.56 h and 1.75 h respectively. Higher river discharge induces stronger ebb velocities and longer ebb than flood duration. SPM levels at station S2 (Fig. 2a) are low with maximum values around 0.17 kg/m 3 . A strong resuspension occurs in S4 station and creates high turbidity conditions near the bed. Main variations of SPM at S4 (Fig. 2e) is quite consistent with variation of currents. Indeed, high values of SPM correspond to high velocities and low values of SPM correspond to low velocities except during the flood very high values of SPM at the bottom (0.73 kg/m 3 ) are associated with low velocities. For spring conditions during high river discharge, tidal variations are illustrated on Fig. 2b (S2) and d (S3) where SPM levels at S2 still rather correspond to fluvial advection (Fig. 2b). Higher concentration is observed near the bottom at S3 (0.68 kg/m 3 ) and this more particularly during the ebb (Fig. 2d).

During the spring tide in a high river discharge period, the turbidity maximum is hitting S3 (KP 15) whereas previous study [START_REF] Berthois | Etude dynamique de la sédimentation dans trois cours d'eau de la Guyane française: la rivière Mahury, la rivière de Cayenne[END_REF]) positioned it downstream Coswine (KP 9). 5.2. Observed intra-tidal dynamics during low river discharge Both surveys in low hydrological conditions coincide with spring tide conditions and two contrasted river discharges (600 m 3 /s and 200 m 3 /s). During moderate discharge (Q 600 m 3 /s), current velocities at station S2 (Fig. 3a) is lower than during the high discharge events (Fig. 2a&b) and the strength of flood and ebb currents are more equivalent. However, at the middle and lower part of the estuary (station S3 and S5) current asymmetry is ebb dominant with maximum values of 1.06 m/s (Fig. 3c) and 1.7 m/s (Fig. 3e), respectively. Concerning SPM, observed levels are increasing from the river mouth (Fig. 3e), they are reaching their maximum (3.94 kg/m 3 near the bottom, Fig. 3c) at station S3 and then they are decreasing until station S2 (Fig. 3a). At station S2 (Fig. 3a), SPM values are lower, with a maximum value of 0.54 kg/m 3 through most of the water column. The SPM variability at station S3 (Fig. 3c) is similar to S2 relying more upon velocity condition but it has a larger difference between surface and bottom layer. At the bottom layer, the SPM variation is in line with those for tidal current. It attains a minimum value at slack water and maximum value at the time of the strongest currents, suggesting a predominance of resuspension and deposition processes. Between stations S3 and S5, some differences in the SPM distribution within the water column can be noticed. At station S5 (Fig. 3e), SPM variation pattern also relies on the current conditions but there is a lag time between the current and the SPM. The lowest SPM levels occur more or less simultaneously as the lowest velocities. Nevertheless, the highest SPM does not occur in phase with the highest velocity. Different patterns are also observed with vertical salinity distributions. At station S2 (Fig. 3b), the whole water column is nearly fresh water with a very low salinity value (0.03 g/kg). At station S3 and S5 (Fig. 3d and f), stratification is observed at HWS while salinity differences between the surface and bottom layers are smaller, indicating a stronger vertical mixing at LWS. The salinity signal at S5 points out a significant variation: salinity remained high around 28 g/kg near the bed at high tide to approximately 6 g/kg during low tide.

For the first survey in the very low hydrological condition (EH1 survey), a long low discharge period (200 m 3 /s) has occurred. Observed vertical variations for current, SPM and salinity at S2 in such dry conditions are illustrated on Fig. 4. The current angle is shifted to isolate along and across the channel component. Only along channel contribution is here plotted on Fig. 4 where negative values correspond to outflow and positive ones to inflow. As in Figs. 3a, 4a displays more balance between flood and ebb. Salinity attains a maximum value of 3.5 g/kg at the high-water slack (Fig. 4c) and a high SPM value of 1.5 kg/m 3 is noticed at the time of the strongest current (Fig. 4b). It should be also noted that during moderate flow rate, HWS are slightly longer than LWS at S2 and S3. For instance, HWS duration reaches 1.17 h and LWS 0.99 h at S2. In case of a more pronounced low river discharge, HWS duration at S2 is increasing up to 1.47 h in regards of 0.47 h for LWS.

Observed longitudinal and seasonal variability

Along-channel monitoring transects are conducted during the low (EH4) and high river discharge (EH3) under mean tidal amplitude. Both surveys lead to contrasted stratification patterns. Fig. 5 presents measured salinity levels along the navigation channel at high and low tide during high river discharge (Fig. 5a &b) and low river discharge (Fig. 5c &d). Transects with low river discharge are extended further upstream while transects at high river discharge are extended more downstream. Therefore, the starting point of transect at the high river discharge is selected as KP0 to facilitate the comparison between two seasons.

Observed flow rate at Apatou is higher than 3500 m 3 /s during the high river discharge (June 2017). As isohaline 5 is clearly visible on Fig. 5a, it is selected to illustrate the seasonal and longitudinal variation.

During the low river discharge (October 2017) discharge is 700 m 3 /s and salt intrusion reaches KP 24 (Fig. 1). Isohaline 5 is oscillating between KP 8 and KP 17 with weak vertical gradient for both low and high tide (Fig. 5c andd). For the high river discharge, this isohaline is oscillating between KP 1 and KP 12 but stays near the bed or mid depth. A low tide, most of the estuary is characterized by a low salinity 0.5 g/kg (Fig. 5b). At high tide, salinity has propagated inside the estuary near the bottom and strong stratification is noticed with a salt wedge until KP 10. Similarly, collected turbidity data provide additional information to the shipboard profile analysis.

During low river discharge (Fig. 6a), SPM level is higher than 0.3 kg/m 3 in the whole water column except at the surface in the most upstream part. It can reach up to 4 kg/m at mid depth. The Maroni estuary appears as turbid from the mouth to KP 15-20 (S3) as already noticed in Fig. 3c. In contrast (Fig. 6b), SPM levels are much lower during high river discharge (0.3 kg/m 3 ). A turbid area around 1.5 kg/m persists near the bottom along the first kilometres. Upstream the salt wedge (KP 10), the water column is both weakly turbid and brackish water. Along the salt wedge, a two-layer behaviour probably happens. Near the bottom, strong vertical variation in SPM is co-located with the salt wedge. SPM is decreasing from 1 to 0.1 kg/m 3 from the bottom to the mid depth. Until the water surface, a fresh water layer with SPM around 0.1 kg/m 3 is flowing above the saline layer.

Numerical analysis of salt intrusion under different river discharge and tidal range

One-year simulation is performed from November 2016 to October 2017 to explore the influence of discharge and tidal range on the saline intrusion and stratification patterns. A 40 days spin up simulation with a constant discharge (mean value of October 2016) was performed in order to initialize the hydrodynamic variables and salinity distribution. Then a one-year simulation with a time series of daily discharge is performed with initial conditions provided by the spin-up simulation. Time evolutions of realistic tidal range and discharge are illustrated on Fig. 7a andb (other subplots are discussed later). It starts with a pronounced dry period about 50 days, followed by a long high river discharge about 250 days and then it finishes with another dry period with moderate flow rates. Extracted events for the analysis match with the four shipboard surveys. For dry periods, saline intrusions are extracted for both discharge 200 m 3 /s, 700 m 3 /s. For each hydrological condition, no significant change in discharge value is observed along the considered neap and spring tidal cycle. For the high river discharge, analysed events are 4790 m 3 /s and 3120 m 3 /s for spring tide whereas lower values 3700 m 3 /s and 3300 m 3 /s are observed for neap tides. Fig. 8 represents the tidally averaged salinity distribution in a single alongchannel section (transect 1 as in Fig. 1).

During river discharge lower than 200 m 3 /s, well-mixed conditions are observed at both spring tide and neap tide (Fig. 8a). Salt water (S 30 g/kg) is only observed for such low discharge and along the 3 first kilometres. For the other discharge configurations, brackish water (S 30 g/kg) is observed inside the estuary. When the discharge rises up to 650 m 3 /s, it generates more vertical variation until approximately km 12 (Fig. 8b). In this condition, brackish water penetrates less into the river than in the case of very low discharge (200 m 3 /s). For instance, isohaline 4 propagated until 30 km in case of very low discharge whereas it only reaches between km 15 and km 17 in case of discharge up to 650 m 3 /s. In contrast, with high discharge conditions, brackish water is generally transported into the estuary during spring tides and it is expelled out of the estuary during neap tides (Fig. 8c,d). The brackish water convergence front remains confined near the mouth during the high discharge. Neap tides of the high discharge also feature significant stratification at the mouth. Stratification is less pronounced during spring tides than during neap tides. Increase of discharge tends to enhance stratified conditions as it can be clearly seen with two cases of neap tides. Indeed, the case with a discharge of 3695 m 3 /s has higher salinity at the bottom than the case with a river discharge of 3300 m 3 /s. The effect of wind on such a pattern would need to be further investigated even if less influence is expected during high flowrates.

Numerical analysis of the residual current and its variability

Tidally-averaged currents are computed in order to estimate the main residual flow direction and to identify the conditions favourable for inflow of salinity and therefore oceanic mud. A single longitudinal view along the navigation channel from the mouth until the upper station S2 is first extracted (Fig. 9) under different tidal ranges and river flows with both low and high discharges. Fig. 9(a, b) shows a complex residual circulation pattern for the low river discharge. Inflow close to the bottom can be observed approximately from river mouth to km 15. Inflow is restricted near the bottom during spring and covers until mid-depth during neap. Flowrate about 700 m 3 /s leads to stronger inflow than with a 200 m 3 /s discharge. Surface residual current is still mainly seawards except between KP 7 to KP 13 (neap cases) where the residual currents are mainly oriented across the channel. From KP 15 to upstream, the residual current is totally ebb dominated except a local circulation noticed at the deepest part KP 22. This area displays islands with trenches and tributaries. For the last kilometres where the depths are shallower, the residual currents are seawards.

During the spring tide with discharge higher than 3000 m 3 /s (Fig. 9c,d), the flow is entirely ebb-directed or fluvial dominated. Strong seaward surface flow associated with immobile bottom layer occurs at some locations along the channel. Residual velocity magnitudes in the shallow areas are much greater than in the deepest parts of the channel. During neap tide and high discharge, residual currents are still mainly seaward even if a circulation zone can be noticed at the mouth. A stronger landward flow is indeed present on the first kilometres from the mouth where stratification pattern is also noticed (Fig. 8c&d).

Discussion

From the results section, different insights related to the Maroni dynamics can be summarized. Under high river discharge conditions (3000 m 3 /s), high turbidity levels are noticed near the bottom along a few kilometres only in the lower estuary (Fig. 6). LWS durations are much longer than HWS (Fig. 2) and residual currents (Fig. 9c &d) are seaward in the whole water column, except at the most downstream area, where a two-layer flow has been noticed. Such high river discharge induces stronger ebb velocities and longer ebb than flood duration. Near the mouth, a local salt wedge close the bottom coincides with fluvial advection near the surface although in the central and upper reaches the fluvial advection dominates the whole water column. This feature is a particularly interesting observation as it supports the existence of two distinct sources of fine sediment. The first one corresponds to a highly concentrated (1 kg/m 3 ) area probably fed mainly by mud bank and shifting seasonally according to flowrate variation. The second one ranging below 0.15 kg/m is brought from upstream by river freshets. Under very low flowrate (200 m 3 /s), the estuary is mostly well mixed, high values of salinity and SPM are observed until upstream S2 station. Up to now, this is the first time that such high values are reported at such an upstream location. Between 2014 and 2016, dry periods have lasted longer than usual and high discharge events have been shorter and weaker [START_REF] Abascal-Zorrilla | Dynamics of the estuarine turbidity maximum zone from landsat-8 data: The case of the Maroni River Estuary, French Guiana[END_REF], which can explain unusual high turbidities. It is hypothesized that the presence of mud until Saint Laurent results mainly from a higher contribution of tidal pumping since HWS durations are much longer than LWS and also from a smaller contribution of bottom inflow. Under moderate low river discharge, EH4 (700-1000 m 3 /s), the estuary can be turbid until KP 15 (Fig. 6). In such a configuration, the HWS durations are slightly higher than the LWS (Fig. 3). Mud presence is probably due to a combination of a small contribution of tidal pumping and a higher contribution of inflow near the bottom (Fig. 9b). These preliminary conclusions need to be further confirmed by a consistent analysis of sediment transport.

From our results, the mouth corresponds to the most active area in terms of sediment dynamics, stratification, residual current. Moreover, it corresponds to the main source of fine sediment and the zone of exchange between the mud bank and the upper reaches of the estuary. It is thus now proposed to first further analyse the seasonal variation of the stratification patterns in this area. Numerical analysis of the residual current also identifies that the inflow in the navigation channel propagates more upstream inside the central part during low river discharges. Therefore, particular attention is then paid, for flow configurations with low river discharge conditions, on: (1) the neap-spring variation at different lateral sections; and (2) the circulation patterns in the central estuary during neap tide. Finally, the obtained results are put in perspective in regards to other regional studies.

Seasonal variations in stratification patterns

Time series of stratification number Sn [-] and residual current U [m/s] are extracted at station S5 and station S4 from the one-year simulation. The seasonal variations in stratification patterns for both stations are plotted in Fig. 7c. At station S5, salinity stratification (Sn) describes a well-marked seasonal and spring-neapvariation controlled by both tidal ranges and river discharges (Fig. 7a&b). Larger tidal ranges reckon more vertical mixing and less stratification. Stratification is more developed under smaller tidal range (neap tides), e.g. day 141 (T m), day 169 (T m) and high river discharge. In the case of extremely low river discharge (day 0 to day 48, river flow less than 400 m 3 /s), the stratification number is very small (average of 0.15) suggesting that the estuary is well-mixed. However, in case of a moderately low river discharge (day 300 to day 350) with river flow between 400 and 1200 m 3 /s, salinity stratification number stands within 0.3 and 1.2 with an average of 0.6. It suggests a partly stratified estuary. In this case, major changes in river discharge has contributed to increase the saline stratification. For river discharge larger than 2660 m 3 /s (day 100 to day 300), stratification number ranges from 0.6 to 1.9 (with an average of 0.94) which corresponds to strong stratification or even salt wedge. The change in stratification number due to flowrate variation exhibits each of three states of stratification: well-mixed, partially mixed and highly stratified. The relationship between stratification number and tidal range and stream flow, was developed by [START_REF] Vijith | A stratification prediction diagram from character-istics of geometry, tides and runoff for estuaries with a prominent channel[END_REF] by an estuarine stratification diagram primary based on tidal range number and runoff number. This diagram has successfully been applied to explain stratification of monsoon Mandovi estuary, which varies from well-mixed to highly stratified. In the case of the Maroni estuary, under high river discharge conditions (river discharge larger than 2660 m 3 /s), the stratification number at station S5 (Sn5_wet) was found to be in relationship with tidal range (T). This relation can be illustrated by Eq. ( 1) as follow: (1)with R and -value 0.05. At station S4, located upstream the converging section and thus already under higher river influence than S5, stratification number Sn features variation from 0 to 1 and displays insignificant correlation with the tidal range. Comparing the evolutions at S4 and S5, the stratification numbers are almost the same for low river discharge and they behave quite differently during high river discharge. At S4, high stratification is observed during discharge within 400-1200 m 3 /s flow (day 300 to day 350). The period from day 300 to day 365 is a dry period but moderate and quite stable flow rates. Thus, salinity intrusion develops further upstream, so the behaviour of stratification at S4 and S5 is quite the same.

When the river flow is very high and coincides with the small tidal range, the whole salt wedge is expelled out of the estuary. Salinity is only observed at S5 which leads to Sn values near zero at S4. Consequently, a higher stratification value of S5 coincides with a minimum value of stratification of S4 (e.g. days 110 and 169, Fig. 7). For day 141, the stratification reaches a maximum value at S5. At S4, the behaviour is less clear since the stratification reaches a maximum and then after a minimum value probably due to significant flowrate variation during the previous days.

In contrast to the stratification number, residual current near the bottom at both station S4 and S5 are controlled by tidal range, stratification number and river discharge. It can be illustrated through a multiple regression comparing residual current near the bottom (US4_bottom, US5_bottom) against tidal range (T), stratification (Sn) and river flow (Q) as Eqs. ((2), and (3)). ( 2)with R andvalue 0.05 (3)with R and -value 0.05.

Residual inflow (positive values) at station S4 mostly occurs when river flow is less than 2660 m 3 /s and tidal range is less than 2.75 m. It strongly depends on tidal ranges as smaller tidal ranges (neap tides, T 1 m) develop stronger inflow near the bottom. The strongest inflow (0.2 m/s) occurs in case of low neap tide (T 0.64 m), stratification of 0.89 and river flow of 900 m 3 /s. Contrarily, outflow mostly occurs during the high river discharge and it is mainly controlled by river discharges. Higher river discharge logically induces higher outflow current since the strongest outflow (-0.25 m/s) can be detected at peak discharge of 7000 m 3 /s (day 110 in time series). More downstream, the bottom residual current at station S5 is mainly directed upstream for a wide range of river discharge both during dry and high river discharge. It is however more marked during dry periods. When the river flow is larger than 2660 m 3 /s, inflow only occurs during neap tides when the tidal range is lower than 2.3 m. Outflow is mostly observed during high river discharge period and sometimes during low river discharge periods. In case of very low flowrate (day 1 to day 48, river flow less than 400 m 3 /s), outflow only occurs when the tidal range is greater than 2.2 m while for moderate flowrates within 400-1200 m 3 /s (day 300 to day 350) outflow only occurs when the tidal range is larger 2.6 m. The strongest inflow at S5 (0.32 m/s) appears at the same time as the strongest inflow at station S4 (in case of low neap tide T 0.64 m, stratification of 0.89 and river flow of 900 m 3 /s). In general, near-bottom residual currents at station S5 are mainly controlled by the tide than by the river flow, since inflow mostly occurs during neap tides and outflow mostly occurs during spring tides.

Processes driving the circulation during low river discharge

Up to now, the circulation has been analysed in a single along estuary transect. This transect is located in the navigation channel in the deeper area and it is not thus representative of the whole cross-section flow. To complete this analysis, lateral views at different cross sections are extracted to further examine the flow pattern and its lateral variation with a moderate low flowrate during the low river discharge for spring (Fig. 10a) and neap tides (Fig. 10c). During spring tide (Fig. 10a), outflow residual current is observed almost along the whole water column at all transects from S5 to S2 with maximum outflow current of 0.2 m/s found at some shallow areas of transect S5, S4 and S3. Outflow mainly happens in the deep channel whereas some inflow occurs over shoals. The barotropic tidal currents seem to mainly control residual current during spring tide. Distributions of residual salinity (Fig. 10b) indicates slight lateral variation from transect S5 to S3 and higher surface salinity compared to salinity level reached in neap tide. Near bottom inflow is observed at the deepest part of the transect S4 where vertical variation in salinity is stronger than in other parts (Fig. 10b). Such inflow could be thus induced by the densitydriven flow.

In contrast during neap tide (Fig. 10c), a two-layer of current can be clearly observed at transect S5, between KP-0.5 and KP-2, with strong inland flow at the bottom and slight outflow near the surface. Inflow currents are also observed in the deepest waters of transect S4 as in spring tides but it is more developed along the water depth and much stronger (from right bank side to KP 1.5) with residual current reaching 0.12 m/s near the bottom. At the left bank side of transect S4, a strong outflow current is observed near the surface (magnitude of -0.15 m/s). Residual circulation is also observed at transect S3 (KP 15) but with slight inflow near the bottom and stronger outflow near the surface. At station S2 (Fig. 10c) in both cases spring and neap tides, flow pattern is almost symmetric with outflow in the main channel while inflow appears at both lateral sides. Such symmetric pattern in exchange flow has also been noticed by [START_REF] Valle-Levinson | Density-driven exchange flow in terms of the Kelvin and Ekman numbers[END_REF] using a semi analytical model with high frictional condition with moderately sloped cross-section. The evidence of the density-driven inflow is also clearly observed during the neap tides. Stronger inflows occurring at the deepest channel at S4 and S5 correspond to a strong vertical variation of salinity in this region. At transect S3 and S4, lateral circulation in velocity can be observed where inflow at some shallow parts occurs with presence of depth variations.

During spring tides, higher tidal range enhances mixing and thus leads to weaker vertical variation in salinity and a reduction of density-driven flow. For instance, at S5 from spring (day 323, T 3 m) to neap tide (day 331, T 0.63 m), Sn is increasing from 0.38 to 1.1. Therefore, weak inflow current is thus observed during spring tides. In contrast, tidally averaged salinity was more stratified during neap tide than during spring tide thus density-driven flow component is overwhelmed which results in a stronger residual circulation. Increase of mixing during spring tides leads to reduced exchange flow as hypothesized by [START_REF] Geyer | Sill processes related to deep water renewal in a fjord[END_REF] and documented in several estuaries [START_REF] Geyer | The dynamics of a partially mixed estuary[END_REF][START_REF] Bowen | Salt transport and the time-dependent salt balance of a partially stratified estuary[END_REF][START_REF] Weisberg | How estuaries work: A Charlotte Har-bor example[END_REF][START_REF] Maccready | Advances in estuarine physics[END_REF][START_REF] Monismith | A simple model of mixing in stratified tidal flows[END_REF][START_REF] Stacey | The tidally aver-aged momentum balance in a partially and periodically stratified estuary[END_REF]. [START_REF] Uncles | The effects of wind, runoff and tides on salinity in a strongly tidal sub-estuary[END_REF] also mentioned an increase of surface salinity at high water because of enhanced vertical mixing in the Tavy estuary (UK) during spring tide. Similarly, stronger stratified condition and associated salt net transport into the estuary has also been observed during neap tides in the Hudson estuary [START_REF] Wang | Mechanisms of tidal oscillatory salt transport in a partially stratified estuary[END_REF][START_REF] Wang | The balance of salinity variance in a partially stratified estuary: Implications for exchange flow, mixing, and stratification[END_REF] or in the Danshuei river in Taiwan [START_REF] Chen | Modeling investigation of asymmetric tidal mixing and residual circulation in a partially stratified estuary[END_REF]. According to [START_REF] Wang | Total exchange flow, entrainment, and diffusive salt flux in estuaries[END_REF], stratification may be regarded as the competition between tidal stirring and mean straining by the exchange flow. Tidal stirring transports salt up from the bottom to the surface, which decreases the stratification. When exchange flow is the greatest during neap tide, tidal stirring is weak. So, the influence of flow exchange exceeds tidal stirring and it thus continues to increase stratification. As tidal amplitude increases (spring tides), the influence of tidal stirring exceeds the exchange flow, so the stratification decreases. Horizontal maps of surface and bottom residual currents are plotted (Fig. 11) to highlight the general circulation (along/across channel component) during neap tide combined with moderate low river discharge (700 m 3 /s). The surface currents (Fig. 11b) are mainly seaward with stronger magnitude along the west channel (Suriname) whereas inflow currents near the bottom (Fig. 11c) are observed in the main channel at the right bank side (French Guiana). These results are in line with observations of [START_REF] Jolivet | Multi-decadal to short-term beach and shoreline mobility in a complex river-mouth environment affected by mud from the Amazon[END_REF] and support the hypothesis of [START_REF] Ross | Intratidal and Subtidal Circulation in a Tropical Estuary during Wet Season: The Maroni, French Guiana[END_REF]. Analysis of bathymetric survey performed by [START_REF] Jolivet | Multi-decadal to short-term beach and shoreline mobility in a complex river-mouth environment affected by mud from the Amazon[END_REF] supplemented by Gardel et al., this issue reveals a relatively straight single channel from the river mouth running north-northeast and a secondary less pronounced channel extending along the Suriname coast (Fig. 1). Based on analysis on ADCP surveys along and across the channel during high river discharge in 2018, [START_REF] Ross | Intratidal and Subtidal Circulation in a Tropical Estuary during Wet Season: The Maroni, French Guiana[END_REF]proposed a simplified diagram of the circulation. They highlight the presence of an ebb channel on the west side and a flood channel on the east side. In our model results, outflow (ebb current) is almost present along the Suriname channel near the mouth. More upstream, the ebb channel crosses the estuary and reaches the east side near the island. Inflow (flood current) enters along the main channel on the east side. Interestingly, the plan views of residual currents at the bottom (Fig. 11c) could also be used to explain the distribution of measured mud thickness in the field. The fresh mud thickness was measured in October 2017 (Fig. 11a) corresponding to the same simulation period. Fresh mud deposits on the east side around the navigation channel occur in a zone characterized by low residual current and located just upstream inflow zone. Mud deposits near the inland seem rather come from across channel exchange from the flood channel to shallow areas.

6.3. In regard to the regional context Despite many studies have focused on the coastal mud bank migration during the last decades, the dynamics of the several estuaries located along the Guiana shoreline are still poorly described. More particularly, few research efforts have focused on interactions between such estuaries and their muddy coastal environment [START_REF] Orseau | Hydro-sedimentary processes of a shallow tropical estuary under Amazon influence. The Mahury Estuary, French Guiana[END_REF][START_REF] Toorman | Interaction of Mangroves, Coastal Hydrodynamics, and Morphodynamics Along the Coastal Fringes of the Guianas[END_REF].

Based mainly on analysis of geographic features, a classification of the estuaries along the Guiana coast has been drawn and four main types of estuaries have been identified [START_REF] Gardel | River estuaries of the Amazon-influenced Guianas coast: diversity and preliminary classification[END_REF]. The first type of estuaries has river mouths oriented perpendicularly to the coast, associated with relatively largedischarge rivers. A subtype of this first type is a transitional river-mouth morphology towards a delta. This is the case for the Maroni and Essequibo estuaries Gardel et al., this issue. The third type of estuaries has low flowrate and its morphodynamic features are thus strongly influenced by the mud bank, and river mouths are diverted westward (the direction of regional alongshore sediment transport) by prograded mud capes and spits. The fourth type of estuaries are fixed by headlands of Precambrian basement rocks. About ten estuaries are spread along the coast of French Guiana. Up to now, more attention has been paid on hydro-sedimentary dynamics of the Mahury (type 4, [START_REF] Orseau | Hydro-sedimentary processes of a shallow tropical estuary under Amazon influence. The Mahury Estuary, French Guiana[END_REF] and Maroni (type 2) estuaries as they host activities. This exploratory study allow to expand the proposed classification with the introduction of physical consideration. In fact, most of the other estuaries belong to type 3 with low flowrate and strong morphodynamic impact of the mud bank. Except Sinnamary estuary and its dam for electricity production, they are less practical reasons to fund their studies and they are thus even less documented. Additional research efforts are thus still needed to provide a recent and complete physical analysis of the Guiana estuaries. Actually, the Maroni estuary is the unique type 2 in French Guiana. Other similar estuaries are Corentyne River between Suriname and Guyana and Essequibo River in Guyana. As the Maroni, these two estuaries are subjected to heavy metal contamination due to gold mining activities [START_REF] Howard | Total mercury loadings in sediment from gold mining and conservation areas in Guyana[END_REF]. More knowledge in circulation may help to better predict the sediment fluxes and remobilization of polluted particles. Similarly, to the Mahury configuration, another mud bank has approached the mouth of the Maroni estuary since 2015 [START_REF] Jolivet | Multi-decadal to short-term beach and shoreline mobility in a complex river-mouth environment affected by mud from the Amazon[END_REF]. Results from the Mahury estuary cannot be fully transposed because both estuaries are quite different in terms of fluvial discharge and geometry features. Because of the strength of Maroni discharge [START_REF] Anthony | The role of fluvial sediment supply and river-mouth hydrology in the dynamics of the muddy, Amazon-dominated Amapá-Guianas coast, South America: a three-point research agenda[END_REF], the mud bank is deviated offshore and it takes more time to cross the mouth. It thus creates a more continuous presence of mud banks at the mouth compared to the other smaller estuaries. According to our results, sediment inflow will occur mainly when the mud bank is near the flood channel on the French Guiana side. When the mud bank migrates through the mouth, it is pushed away by the river and then it by-pass the ebb channel on the Suriname side. Less mud inflow is thus expected. This assumption needs to be further investigated since offshore the mud-wave interaction becomes more significant and more research efforts are thus needed to analyse this effect on flow circulation. Even if the Maroni displays sandier bed sediment than the other Guiana estuaries, muddy materials and higher salinity level have been observed up to Saint Laurent during a well pronounced low river discharge in 2016. During drier year that would probably happen more often in a near future due to climate change, this estuary can be as affected as the other estuaries by a mud bank presence. Similarly, as on the Mahury, the river flowrate also appears as a key parameter controlling the dynamics [START_REF] Orseau | Decadal-scale morphological evolution of a muddy open coast[END_REF].

Conclusions and perspectives

Field surveys have been conducted under low and high river discharge season for different tidal conditions. To enlarge the analysis, a 3D hydrodynamic model has been used to determine stratification patterns and associated residual currents under a wide range conditions.

Tidal data reckon an increase of the tidal amplitude in the downstream part of the estuary due to convergence. Further upstream friction effect dominates and the tidal range decreases. From in-situ measurements, a well contrasted behaviour has been observed between the low and high river discharge periods. During the high river discharge period, the river dominates estuarine dynamics, with stronger ebb currents at all measurement stations. Salinity is only observed near the mouth during high tide and the estuary is nearly fresh during low tide. The along channel in situ survey has pointed out a turbidity maximum which seems to persist at the bottom near the mouth during high river discharge. Near the surface, an upper layer with lower SPM and salinity levels is observed. During the low river discharge period, the estuary appears highly turbid until the central reaches.

The model results identify a well-mixed estuary during very low river discharge (river discharge lower than 400 m 3 /s), and it turns into partially stratified estuary under moderately low river discharge (river discharge ranging between 400 m 3 /s and 1200 m 3 /s) and it becomes strongly stratified or salt wedge during the high river discharge period (river discharge is greater than 2600 m 3 /s). Residual inflow near the bottom along navigation channel mostly occurs during the low river discharge period when the estuary is between well-mixed or partly stratified. Stronger inflow currents are more developed during neap tides with moderately low river discharge due to an increase of density-driven flow. In fact, the strongest inflow current is developed in case of low neap tide with a river discharge of 800-900 m 3 /s. Under such flowrate conditions in neap tide, residual currents are landward from the bottom to mid depth until the first KP15 from the mouth. The extension of the inflow area matches with the zones where high concentration level and mud deposit have been observed. Inflow channel starts from the location of the mud bank near the mouth and extends along the navigation channel in the eastern part. This most favourable flow pattern for mud income however requires that sediments are available and erodible for such flow conditions. Developments on the model are ongoing to include sediment transport and the wave influence. Once, it would be interesting to analyse how these numerical results evolve once the sediment dynamics and associated stratification effect are added inside the model. Further efforts are still needed to analyse the influence of the tributaries and the mangrove on the circulation and to characterize the estuarine dynamic upstream Saint Laurent.

CRediT authorship contribution statement

Fig. 1 .

 1 Fig. 1. The Maroni estuary. 1a bathymetry and overall location. 1b survey stations and main landmarks.

Fig. 2 .

 2 Fig. 2. Vertical variations during high river discharge. (a) S2 neap tide; (b) S2 spring tide (c) S3 neap tide, (d) S3 spring tides, (e) S4 neap tide, (f) Salinity at S4 during neap tide.

Fig. 3 .

 3 Fig. 3. Vertical variations of current velocity, salinity, and SPM at stations S2 (a&b), S3 (c&d) and S5 (e&f) during October, 2017 field campaign (low river discharge, spring tides).

Fig. 4 .

 4 Fig. 4. Along channel velocity, SPM and salinity at S2 during pronounced low river discharge (EH1).

Fig. 5 .

 5 Fig. 5. Measured salinity levels measured along the navigation channel at high and low tide during wet (a, b) and dry season (c, d).

Fig. 6 .

 6 Fig. 6. Measured SPM levels measured along the navigation channel at high tide during dry and high river discharge.

Fig. 10 .

 10 Fig. 10. Distribution of longitudinal residual current and residual salinity in cross section during the low river discharge EH4 (Positive values correspond to landward current and

  Between 2014 and 2018, a mud bank has crossed the Mahury estuary[START_REF] Orseau | Decadal-scale morphological evolution of a muddy open coast[END_REF].[START_REF] Orseau | Hydro-sedimentary processes of a shallow tropical estuary under Amazon influence. The Mahury Estuary, French Guiana[END_REF] have performed in situ monitoring of the Mahury estuary between 2013 and 2016. Their analysis based on residual transport pointed out inflow of sediment fluxes during the low river discharge and still some inflow during high river discharge at the mouth for spring tide. According to[START_REF] Orseau | Decadal-scale morphological evolution of a muddy open coast[END_REF], the mud bank near the Mahury estuary took almost 4 years to migrate across the mouth and only one bank has by-passed the estuary during the 10 years of observation.

  Performing model simulation, Data analysis, Graphical visualisation, Drafting the manuscript. Aldo Sottolichio: Conceptualization and design of the study, Data interpretation, Manuscript critical review and editing. Nicolas Huybrechts: Performing model simulation, Data analysis, Graphical visualisation, Drafting the manuscript. Antoine Gardel: Conceptualization and design of the study, Data interpretation, Manuscript critical review and editing.

Table 1 .

 1 Overview of structure of the hydrodynamic simulation considering seasonal river flow for calibration and verification.

	Calibration/Validation Scenarios	Name River discharge	Station/survey	Tide
			(m 3 /s)		date	characteristic
			Maroni	Mana
	Calibration	High river	EH3 3850/3610 741/696 S2(14th)	Neap tides
		discharge			S3(13th)
		(June 2017)			S4(13th)
		Low river	EH4 582	78	S2(8th)	Spring tides
		discharge			S3(8th)
		(October 2017)			S5(8th)
	Verification	Low river	EH1 176/182	71/65	S2 (17th)	Spring tides
		discharge			S3(15th)
		(November
		2016)
		High river	EH2 4770/4540 485/422 S2(15th)	Spring tides
		discharge			S3(14th)
		(March 2017)

Table 2 .

 2 Comparison between model results and observations in calibration.

		Parameters	RMSE			Skill
			Station	Surface	Bottom	Surface	Bottom
	EH3 Calibration	Water level (m)	SLM	0.20		0.96
			Crique Vach
		Velocity (m/s)	S2	0.03	0.18	0.98	0.77
			S3	0.14	0.07	0.93	0.93
			S4	0.05	0.14	0.89	0.74
		Direction ()	S2	19.73	14.47	0.96	0.95
			S3	34.72	31.39	0.89	0.91
			S4	32.55	9.55	0.89	0.96
		Salinity (g/kg)	S2	0.02	0.02	0.00	0.00
			S3	0.02	0.02	0.00	0.00
			S4	0.41	0.71	0.59	0.91

Table 3 .

 3 Comparison between model results and observations in verification.

		Parameters	RMSE			Skill
			Station	Surface	Bottom	Surface	Bottom
	EH1 Verification	Water level (m)	SLM	0.06		0.98
			Crique	0.10		0.98
			Vache
		Velocity (m/s)	S2	0.08	0.16	0.76	0.53
			S3	0.16	0.08	0.83	0.82
		Direction ()	S2	31.49	25.66	0.92	0.92
			S3	57.55	16.16	0.58	0.93
		Salinity (g/kg)	S2	1.39	1.29	0.61	0.69
			S3	4.32	3.99	0.69	0.76
	4.1. Field survey
	Four shipboard profiling surveys (EH1 to EH4) were conducted between 2016 and 2017 during low and
	high river discharges with different flow conditions in terms of river discharge and tidal range (Table 1).
	Two stations (S2 at KP 32, S3 at KP 15 Fig. 1) are monitored during four surveys (EH1, EH2, EH3, and
	EH4). Another two stations located more downstream (S4 at KP 6 and S5 at KP 2) are added for surveys
	EH3 and EH4. During the first three surveys (EH1, EH2 and EH3), station S1 and S2 were sampled
	during two successive days (Table

  Table 3 points out that the model results reasonably agree with the observed data for water level and velocity. The model skill score of water level (EH1) indicates the SS are almost unity (0.98) in both stations, SLM and Crique Vache. The RMSE of water levels is 0.06 m at Crique Vache and 0.1 m at SLM. The model skill for velocity at station S2, S3 and S4 at both surface layer and bottom layer during high river discharge of calibration (

Acknowledgements

The authors would like to thank the "Service d'Hydrographie Océanique Maritime (SHOM)" for providing bathymetric data on the continental shelf, the Direction de l'Equipement de l'aménagement et du logement de la Guyane (DEAL)" for the bathymetric data inland, tidal data and their financial support. We are also grateful to Sylvain Morvan, Tanguy Maury, Sandric Lesourd and Guillaume Detandt who helped with data collection. Funding was also provided by the European Fund for Regional Development (ERDF) programme OYAMAR and by the French Guiana Office of Water under the EFHEMAR project to support the in situ work. Anh, T.K. Do, post doc position has been funded by the Inthrig project from ANR Carnot Cerema Effiscience.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.


Franck Ngassam

Etienne Urbain

Loic Joly

Samy Boukari

Jacek Arabski

François Bertran

Patrick Le Fèvre

Guillaume Garreau

Patrick Wetzel

Mebarek Alouani

Martin Bowen

Wolfgang Weber

Fluorinated Phthalocyanine Molecules on Ferromagnetic Cobalt: a Highly Polarized Spinterface

Spin-resolved photoemission spectroscopy experiments are performed on perfluorinated

Co-phthalocyanine (F 16 CoPc) deposited onto ferromagnetic Co(001) to examine how doping (here with fluorine) of an organic semiconductor influences the interfacial electronic properties, and whether the formation of highly spin-polarized interface states is possible. It is found that this later property, initially reported for the non-fluorinated Pc, is also present for the fluorinated system Co/F 16 CoPc. This result shows that doping an organic semiconductor, which is an important and effective method to tailor the electronic transport properties of the molecules, does not inhibit the presence of a highly polarized spinterface.

Introduction

Organic spintronics, which blends spin electronics with organic/molecular electronics, 1 has recently received considerable attention (e.g. [START_REF] Scheybal | Induced Magnetic Ordering in a Molecular Monolayer[END_REF][START_REF] Wende | Substrate-Induced Magnetic Ordering and Switching of Iron Porphyrin Molecules[END_REF][START_REF] Iacovita | Visualizing the Spin of Individual Cobalt-Phthalocyanine Molecules[END_REF][START_REF] Dediu | Spin Routes in Organic Semiconductors[END_REF][START_REF] Atodiresei | Design of the Local Spin Polarization at the Organic-Ferromagnetic Interface[END_REF][START_REF] Barraud | Unravelling the Role of the Interface for Spin Injection into Organic Semiconductors[END_REF][START_REF] Raman | From Interface-Engineered Templates for Molecular Spin Memory Devices[END_REF][START_REF] Editorial | A molecular jigsaw puzzle[END_REF][START_REF] Cornia | The molecular way[END_REF][11] ) because of the prospect of developing a new generation of spin devices toward information technology. In contrast to the class of inorganic semiconductors, where only relatively few semiconductors are employable, hundreds of new semiconducting molecules produced and screened out so far suggest a large number of applicable materials.

A very attractive aspect of organic semiconductors (OS) is the ability to tune the semiconductive behavior via a simple chemical substitution, e.g. by replacing the H atoms by halogen atoms such as fluorine (F). In this way, the energy position of molecular orbital levels across metal-organic semiconductor (MO) and organic-organic semiconductor (OO) interfaces can be tuned. Since molecular orbital offsets define energy barriers that control carrier injection into, and transport between, layers, their control is thus of key importance for organic thin film devices such as OLEDs and photovoltaic cells. [START_REF] Armstrong | Organic/organic heterojunctions: Organic light emitting diodes and organic photovoltaic devices[END_REF] The interfaces between molecular films and contacting materials are crucial, such that interface engineering, i.e. the control of interfacial electronic properties, is a necessary prerequisite toward further progress in organic electronics. In this vein, numerous studies have investigated the electronic band structure of ferromagnetic (FM) MO-interfaces, the so-called spinterfaces, and identified spin-polarized interface states (IS) within the band gap region of the OS. [START_REF] Methfessel | Spin Scattering and Spin-Polarized Hybrid Interface States at a Metal-Organic Interface[END_REF][START_REF] Lach | Metal-Organic Hybrid Interface States of a Ferromagnet/Organic Semiconductor Hybrid Junction as Basis for Engineering Spin Injection in Organic Spintronics[END_REF][START_REF] Müller | Spin-Dependent Electronic Structure of the Co/Al(OP) 3 Interface[END_REF][START_REF] Lin | Tuning Gap States at Organic-Metal Interfaces via Quantum Size Effects[END_REF][START_REF] Droghetti | Electronic and Magnetic Properties of the Interface between Metal-Quinoline Molecules and Cobalt[END_REF][START_REF] Shi | Hybrid Interface States and Spin Polarization at Ferromagnetic Metal-Organic Heterojunctions: Interface Engineering for Efficient Spin Injection in Organic Spintronics[END_REF] The high spin polarization of these states at room temperature (RT) was observed by spin-resolved photoemission spectroscopy, for a number of systems (Co(001)/Pc, 19 Co(001)/amorphous C, [START_REF] Djeghloul | Highly Spin-Polarized Carbon-Based Spinterfaces[END_REF] Co(001)/phenanthroline, [START_REF] Djeghloul | High Spin Polarization at Ferromagnetic Metal ŰOrganic Interfaces: A Generic Property[END_REF] Co(001)/pentacontane, [START_REF] Djeghloul | High Spin Polarization at Ferromagnetic Metal ŰOrganic Interfaces: A Generic Property[END_REF] Fe(001)/Pc, [START_REF] Djeghloul | High Spin Polarization at Ferromagnetic Metal ŰOrganic Interfaces: A Generic Property[END_REF] Fe(001)/C 60 [START_REF] Djeghloul | High Spin Polarization at Ferromagnetic Metal ŰOrganic Interfaces: A Generic Property[END_REF] ). The spinterface magnetism may be controlled electrically using either an adjacent artificial magnetoelectric, [START_REF] Studniarek | Modulating the Ferromagnet/Molecule Spin Hybridization Using an Artificial Magnetoelectric[END_REF] or using ferroelectric molecules. [START_REF] Liang | Ferroelectric Control of Organic/Ferromagnetic Spinterface[END_REF] The spinterface magnetism and spin polarization may also be established across noble metal spacers. [START_REF] Gruber | Spin-Dependent Hybridization between Molecule and Metal at Room Temperature through Interlayer Exchange Coupling[END_REF][START_REF] Urbain | Cu Metal/Mn Phthalocyanine Organic Spinterfaces atop Co with High Spin Polarization at Room Temperature[END_REF] Finally, the high transport spin polarization at RT of the Co/C spinterface was also experimentally demonstrated. [START_REF] Katcko | Spin-driven electrical power generation at room temperature[END_REF] At low temperatures spin-polarized scanning tunneling microscopy on a single CoPc molecule adsorbed on a FM Fe film showed a significant spin dependence of tunneling current flow. [START_REF] Brede | Spin-and Energy-Dependent Tunneling through a Single Molecule with Intramolecular Spatial Resolution[END_REF] The electronic character of the OS studied in the above investigations is mainly determined by C-C, C-H and a few C-N bonds. The Pauling electronegativity of H (2.1) and N (3) are relatively close to that of C (2.5), [START_REF] O'hagan | Understanding organofluorine chemistry. An introduction to the C-F bond[END_REF] such that the charge transfer within the C-H and the C-N bonds is supposed to be small. In fluorinated OS, however, the high electronegativity of F (4) leads to electrically highly polarized C-F bonds, with the electron density substantially on F. [START_REF] O'hagan | Understanding organofluorine chemistry. An introduction to the C-F bond[END_REF] Of particular interest is the lowering of the molecular orbitals energies close to the Fermi level upon fluorination, leading to an increase in the molecule's ionization potential and electron affinity. [START_REF] Babudri | Fluorinated organic materials for electronic and optoelectronic applications: the role of the fluorine atom[END_REF][START_REF] Brinkmann | Fluorinated phthalocyanines as molecular semiconductor thin films[END_REF] For example, fluorinated Cu-phthalocyanine (F 16 CuPc) exhibits a preferred acceptor behavior and has been widely used as an n-type semiconductor in organic electronics. [START_REF] Jiang | Organic photovoltaic cells using hexadecafluorophthlaocyaninatocopper (F 16 CuPc) as electron acceptor material[END_REF][START_REF] Jea | An organic microcrystal array-embedded layer: Highly directional alternating p-and n-channels for ambipolar transistors and inverters[END_REF][START_REF] Li | Recent advances in one-dimensional organic p-n heterojunctions for optoelectronic device applications[END_REF][34] While a series of (spinintegrated) photoemission studies of fluorinated OS on coinage metals (Cu, Ag, Au) exist (see [START_REF] Rückerl | Particular electronic properties of F 16 CoPc: A decent electron acceptor material[END_REF] and references therein), no such studies are reported for fluorinated molecules on FM transition metals such as Co. The goal of the present study is to show how doping an OS by substituting H by fluorine influences the interfacial electronic properties, and whether the formation of highly spin-polarized IS is still possible.

3

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Methods

Spin-resolved photoemission experiments at room temperature were undertaken on the Cassiopée beamline at Synchrotron Soleil using p-polarized photons of 20 eV energy impinging on the sample at 45 o . We emphasize that no significant photon-induced beam damage to the molecules could be evidenced. The spin polarization of the photoelectrons, which were collected in normal emission geometry, was measured using a Mott detector with an effective Sherman factor S of 0.12. The Mott detector exploits the left-right asymmetry A of electron scattering due to spin-orbit coupling to measure the polarization of an electron beam. [START_REF] Kessler | Polarized Electrons[END_REF] The energy and the angular resolution of the energy analyzer was 130 meV and 7 o , respectively. In order to eliminate experimental asymmetries due to a misalignment of the electron beam with respect to the Mott detector, photoemission spectra for opposite magnetization directions were measured. The spin polarization component P n perpendicular to the scattering plane is given by P n = A/S. The spin-up and spin-down intensity spectra were obtained as follows: I up = I 2 (1 + P n ) and I down = I 2 (1 -P n ) with I the spin-integrated photoemission signal.

To extract the spin-resolved photoemission signal (difference spectrum) that comes from the ISs and from the molecular layers atop the interface, we used a subtraction procedure that takes into account the molecule-induced attenuation of the Co substrate photoemission signal. This procedure and its justification are presented in detail in Refs. [19][START_REF] Djeghloul | Highly Spin-Polarized Carbon-Based Spinterfaces[END_REF][START_REF] Djeghloul | High Spin Polarization at Ferromagnetic Metal ŰOrganic Interfaces: A Generic Property[END_REF] The density functional theory (DFT) calculations were carried out by means of the Vienna ab-initio simulation package (VASP) [START_REF] Kresse | Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[END_REF] and the generalized gradient approximation for exchangecorrelation potential as parametrized by Perdew, Burke, and Ernzerhof. [START_REF] Perdew | Generalized Gradient Approximation Made Simple[END_REF] We used the projector augmented wave (PAW) pseudopotentials as provided by VASP. [START_REF] Kresse | From ultrasoft pseudopotentials to the projector augmented-wave method[END_REF] The van der Waals (vdW) weak interactions were computed within the so called GGA-D2 approach developed by Grimme [START_REF] Grimme | Semiempirical GGA-type density functional constructed with a long-range dispersion correction[END_REF] and later implemented in the VASP package. [START_REF] Bucko | Improved description of the structure of molecular and layered crystals: ab initio DFT calculations with van der Waals corrections[END_REF] A kinetic energy cutoff of 450 eV has been used for the plane-wave basis set. To take into account the correlation effects of transition-metal 3d electrons, the DFT-GGA+U method 42 is adopted and in which the Hubbard U-term was chosen to be 3 eV in all cases. Charge transfer and local magnetic moments were calculated using a Bader charge analy-4 Page 4 of 20

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The Journal of Physical Chemistry sis. [START_REF] Bader | Molecular Charge Distributions and Chemical Binding[END_REF][START_REF] Tang | A grid-based Bader analysis algorithm without lattice bias[END_REF] For the calculations one molecule was placed on a Co(100) slab simulated by three atomic layers of a 8x8 lateral super-cell intercalated by seven vacuum layers in the vertical direction.

All experiments were performed in-situ in ultrahigh vacuum systems with a base pressure in the low 10 -10 mbar range. In the first step of the sample preparation ferromagnetic Co films of 15 ML thickness have been deposited on a Cu(001) single crystal at room temperature from a rod heated by electron beam bombardment at a deposition rate of about 1 ML/min. Prior to deposition, the Cu surface was cleaned by several cycles of Ar-ion sputtering and annealing at 800 K. The film system Cu(001)/Co has been extensively investigated in the past (see for instance Refs. [START_REF] Clarke | A LEED Determination of the Structure of Cobalt Overlayers grown on a Single-Crystal Cu(001) Substrate[END_REF][START_REF] Krams | Magnetic Anisotropies of Ultrathin Co(001) Films on Cu(001)[END_REF][START_REF] Heckmann | Crystallographic Structure of Cobalt Films on Cu(001): Elastic Deformation to a Tetragonal Structure[END_REF][START_REF] Ramsperger | Growth of Co on a Stepped and on a Flat Cu(001) Surface[END_REF] ). Co films on Cu(001) are magnetized remanently in-plane along the [110]-direction.

In the second step of the sample preparation we deposited a thin film of CoPc or F 16 CoPc (both purchased from Aldrich) onto the ferromagnetic film at room temperature. The organic molecules are evaporated by radiative heating and the evaporation rate is controlled by a quartz microbalance. The evaporation rate of the organic films was determined to be around 1 ML/10 min. For the measurements of the work function change the effective rate was much slower as the deposition steps were interrupted by the measurements. The thicknesses of the molecular layers were determined by Auger electron spectroscopy as well as by studying the reflectivity of electrons as a function of molecular coverage in electron reflection experiments (not shown; similar to experiments in ref. [START_REF] Djeghloul | Breakdown of the Electron-Spin Motion upon Reflection at Metal-Organic or Metal-Carbon Interfaces[END_REF] ). The similar molecular stability of CoPc and F 16 CoPc suggests that the successful adsorption of intact CoPc molecules onto Co surfaces [START_REF] Takács | Electron transport through single phthalocyanine molecules studied using scanning tunnelling microscopy[END_REF] is also straightforwardly expected for F 16 CoPc.

Results and discussion

The high electronegativity of the F atoms in the fluorinated Pc molecules is supposed to have a significant impact on the strength of the interfacial dipole that is created at the Co/F 16 CoPc interface. The presence of an interface dipole is signaled, using electron reflection spectroscopy, by an energy shift of the secondary electron cut-off. Figure 1 The behavior of ∆ϕ for the non-fluorinated Pc is similar to what was already observed in the past for the same system Co(001)/CoPc 49 as well as for a similar system, namely Cu(001)/MnPc. [START_REF] Djeghloul | Breakdown of the Electron-Spin Motion upon Reflection at Metal-Organic or Metal-Carbon Interfaces[END_REF] In all cases a monotonous decrease of ∆ϕ down to values of about -1.2 eV for Co/CoPc and -0.9 eV for Cu/MnPc is found.

It is emphasized that within a simple picture we would expect that the value of ∆ϕ , in particular its sign, reflects the total charge transfer (CT) at the molecule-substrate interface. Our DFT calculations show that electronic charge is transferred from the Co substrate to the molecule for both the non-fluorinated and the fluorinated molecules (3.7 electrons (e -) for CoPc; 5.3 e -for F 16 CoPc; see table) such that we would expect in both cases rather an increase of the work function, i.e. ∆ϕ > 0. However, whether the work function decreases or increases does not only depend on the direction of the overall charge transfer. The situation is in general more complicated. This problem has been already discussed by Javaid et al. [START_REF] Javaid | Chemisorption of manganese phthalocyanine on Cu(001) surface promoted by van der Waals interactions[END_REF] In fact, one has to go beyond the standard dipole model and to examine how the charge is spatially distributed across the interface. The es-6

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The Journal of Physical Chemistry sential point is that, rather than having a rigid shift in molecular orbitals, the interface dipole in fact consists of Friedel-like oscillations that more realistically reflect how the metal is screening the interface charge due to molecular adsorption. ). We thus expect the difference in ∆ϕ not to be too dramatic between the two molecules. This is what we observe in the low-coverage regime.

For larger coverage, however, we observe an increase of ∆ϕ in the case of F 16 CoPc.

We emphasize that a similar difference in the behavior of ∆ϕ was observed for the same organic molecules but deposited onto polycrystalline Au. [START_REF] Petraki | CoPc and CoPcF16 on gold: Site-specific charge-transfer processes[END_REF] While ∆ϕ of CoPc continues decreasing for thicknesses above 1 ML (corresponds to about 0.4 nm), an increase is found for F 16 CoPc. A careful analysis of this problem leads to the conclusion that the work function changes for larger thicknesses are driven by the adjustment of the chemical potentials to equilibrium at the interface between the metal substrate and the formed Pc film. [START_REF] Petraki | CoPc and CoPcF16 on gold: Site-specific charge-transfer processes[END_REF] To study the spin-resolved electronic structure at the interface between F 16 CoPc and the FM Co substrate, we performed spin-resolved photoemission spectroscopy experiments. We present in Fig. 2 2

). These structures are similar to those that were already observed in recent experiments on nonfluorinated Pc, on other organic molecules as well as on amorphous carbon and were identified as highly polarized IS. [19][START_REF] Djeghloul | Highly Spin-Polarized Carbon-Based Spinterfaces[END_REF][START_REF] Djeghloul | High Spin Polarization at Ferromagnetic Metal ŰOrganic Interfaces: A Generic Property[END_REF] To more directly evidence the additional features in the spectra, we examine spin-polarized difference spectra so as to focus on the spin-resolved photoemission signal that arises from the interface and the molecular layers atop the interface. [19][START_REF] Djeghloul | Highly Spin-Polarized Carbon-Based Spinterfaces[END_REF][START_REF] Djeghloul | High Spin Polarization at Ferromagnetic Metal ŰOrganic Interfaces: A Generic Property[END_REF] Figure 3 shows the energy dependence of spin-polarized difference spectra at room temperature for 1.3 ML (top) and 2 ML F 16 CoPc on Co (middle) as well as of the spin polarization of the difference spectra for 2 ML F 16 CoPc on Co (bottom). The intensity close to the Fermi level is dominated by a spin-up structure whose maximum is at -0.25 eV energy. The spin-down channel, on the other hand, exhibits a small gap.

Consequently, the spin polarization of the interfacial electronic band structure is strongly positive close to the Fermi level. At higher binding energy, around -0.8 eV, we observe a strongly negatively polarized state.

By comparing the difference spectra obtained with the fluorinated Pc molecules (Fig. 3) with those of non-fluorinated ones (MnPc and H 2 Pc 19 ) we find good agreement: For F 16 CoPc on Co the binding energy positions of the IS are -0.3 and -0.8 eV compared to -0.3 and -1 eV for MnPc and H 2 Pc. The energy position of the IS at higher binding energy may be influenced by the position of the HOMO, which lies in this energy range and can slightly change its position upon fluorination 53 and depends as well on the choice of the central metal ion. [START_REF] Grobosch | Engineering of the Energy Level Alignment at Organic Semiconductor Interfaces by Intramolecular Degrees of Freedom: Transition Metal Phthalocyanines[END_REF] Concerning the -0.25 eV peak, the line widths (FWHM) are for fluorinated and non-fluorinated Pc around 0.5 eV. We emphasize 8

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The Journal of Physical Chemistry that similar energy positions and line widths were also observed for other non-fluorinated organic molecules on Co(001). [START_REF] Djeghloul | High Spin Polarization at Ferromagnetic Metal ŰOrganic Interfaces: A Generic Property[END_REF] We corroborate the above experimental finding that the interface between a FM metal and fluorinated and non-fluorinated Pc molecules exhibits a very similar density-of-states structure thanks to DFT calculations. While the differences between CoPc and F 16 CoPc become more important for binding energies below -1.5 eV, no significant differences are found in the energy region closer to the Fermi level. This is thus in line with the experimental fact that both molecules on top of Co(001) possess very similar interfacial spectral features. We emphasize in this context that claims exist in the literature (see [START_REF] Rückerl | Particular electronic properties of F 16 CoPc: A decent electron acceptor material[END_REF]

Conclusion

In conclusion, we performed spin-resolved photoemission spectroscopy experiments on pacts the formation of highly spin-polarized IS close to the Fermi level. We find that this property, initially reported for the non-fluorinated Pc, also appears for the fluorinated system F 16 CoPc on Co. This result is particularly interesting from the application point of view since it shows that doping (here with fluorine), which is an important and effective method to tailor the electronic transport properties of a system, does not inhibit the presence of a highly polarized spinterface.

Acknowledgement

We gratefully acknowledge support from the CNRS, the Institut Carnot MICA's 'Spinterface' grant, from ANR grant ANR-11-LABX-0058 NIE and from the Franco-German university. We thank the SOLEIL staff for technical assistance and insightful discussions. The DFT calculations were performed using HPC resources from GENCI-CINES Grant 2018-gem1100 and from Strasbourg HPC mesocenter.

Note:

The authors declare no competing financial interest.

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Figure 1 :

 1 Figure 1: Change of the work function of CoPc (open symbols) and F 16 CoPc (filled symbols) on Co(001) for different Pc coverage.

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 720 the spin-resolved electron distribution curves as a function of the binding energy for Paragon Plus Environment The Journal of Physical Chemistry the uncovered Co film (top), the Co film covered by 1.3 ML F 16 CoPc (middle), and the Co film covered by 2 ML F 16 CoPc (bottom). When studying only the Co(001) (top) surface, we observe a strong imbalance of the spin-up and spin-down channels resulting from the FM Co layer, which corresponds to a strong negative spin polarization close to the Fermi level. When Co is covered by F 16 CoPc (middle and bottom), the photoemission signal is attenuated in both spin channels. Apart from this we observe the appearance of two new structures: one at around -0.25 eV in the spin-up channel, and another at around -0.8 eV in the spin-down channel (both indicated by arrows in Fig.

Figure 2 : 9 PageFigure 3 :

 293 Figure 2: Spin-resolved photoemission spectra as a function of the binding energy for 15 ML Co on Cu(001) (top), 1.3 ML F 16 CoPc on Cu(001)/Co (middle), and 2 ML F 16 CoPc on Cu(001)/Co (bottom). The photon energy is 20 eV. The arrows in the middle and bottom panel indicate the appearance of spin-polarized IS.

Figure 4 10 Page 10 of 20 ACS

 41020 shows the calculated spin-polarized density of the molecules' Paragon Plus Environment The Journal of Physical Chemistry p-states for Co(3 ML)/CoPc(1 ML) (black line) and for Co(3 ML)/F 16 CoPc(1 ML) (green line).

Figure 4 :

 4 Figure 4: Calculated spin-polarized density of the molecules C p-states for Co(3 ML)/CoPc(1 ML) (black line) and for Co(3 ML)/F 16 CoPc(1 ML) (green line). All DOS data have been averaged over an energy interval of 50 meV.

Table 1 :

 1 Site-specific charge transfer in units of the elementary charge for the systems Co/CoPc and Co/F 16 CoPc

		CoPc F 16 CoPc
	Co (1)	-0.31	-0.3
	C (32)	-3.97	-5.29
	N (8)	-0.04	+0.34
	H (16)	+0.61	-
	F (16)	-	+0.03
	total charge -3.71	-5.22

The behavior of ∆ϕ for the fluorinated Pc, on the other hand, is quite different as it exhibits a non-monotonous behavior. While ∆ϕ exhibits a decrease similar to that of CoPc up to a thickness of about one ML, ∆ϕ increases for higher F 16 CoPc coverage. In fact, the contribution of the F atoms in F 16 CoPc is not so important. While the 16 H atoms in the CoPc lead to a CT from the molecule to the substrate of 0.61 e -(see table) the 16 F atoms in F 16 CoPc are at the origin of a CT in the same direction of only 0.03 e -(see table

  and references therein) that the charge transfer, which occurs at a different interface, namely F 16 CoPc on Au, is limited to the Co center of the molecule and therefore hardly affects the ligand orbitals of the molecule. If the same were happening in the case of the systems Co/CoPc and Co/F 16 CoPc, it would not be surprising to see only little differences between these two systems for the p-states in an energy region close to the Fermi level. However, our calculations (not shown) in which we determined the charge transfer between Co(001) as substrate and three organic molecules (CoPc, F 16 CoPc, and H 2 F 16 Pc) show that this is not the case. For all three molecules the dominant contribution to the charge transfer, in which electrons are transferred from the Co substrate to the molecules, comes from the 32 C atoms (3.97 e -for CoPc, 5.29 e -for F 16 CoPc, and 3.97 e -for H 2 F 16 Pc). The contribution from the single central Co ion in CoPc and F 16 CoPc is only 0.3 e -. Within the DFT calculations, we also studied the magnetization of the ligand and the central Co ion in both molecules. While the net magnetization of the ligand is antiparallel oriented with respect to the magnetization of the Co substrate with a magnetic moment of 0.39 µ B for CoPc and 0.57 µ B for F 16 CoPc), the magnetization of the central Co ion is parallel oriented with respect to the substrate magnetization (0.43 µ B for CoPc, 0.79 µ B for F 16 CoPc).

	The charge transfer is thus distributed over the entire molecule, including the central metal ion if
	any is present.

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