**Spatial Cadmium Distribution in the Charente Watershed and Potential Risk Assessment for the Marennes Oleron Bay (Southwest France)**

Coynel Alexandra, Khoury Alaa, Dutruch Lionel, Blanc Gérard, Bossy Cécile, Derriennic Hervé and Schäfer Jörg *University of Bordeaux, EPOC, UMR 5805, Talence France* 

#### **1. Introduction**

20 Novel Approaches and Their Applications in Risk Assessment

WHO (World Health Organization). (1985). Guidelines for the study of dietary intakes of chemical contaminants, WHO Offset Publication, n° 87, Geneva, Switzerland, 104 p. WHO (World Health Organization). (1995). GEMS/Food-EURO Second Workshop on

EUR/ICP/EHAZ.94.12/WS04-FSR/KULREP95.

Reliable Evaluation of Low-Level Contamination of Food, Kulmbach, Germany,

In recent years, high levels of pollutants in coastal ocean waters and in the marine food chain have been attributed to inputs either via the atmosphere (Nriagu, 1989) or by direct inputs from rivers and estuaries (e.g. Millward et al., 1996; Baeyens et al., 1997; Chiffoleau et al., 1999). In fact, rivers are considered as a major pathway for the organic and inorganic contaminant transfers from the continent to the ocean, especially during flood events (e.g. Coynel et al., 2007).

The Marennes Oleron Bay (MOB) is the first oyster-producing area in France providing nearly half of the oysters commercialised (Goulletquer & Héral, 1997; Soletchnik et al., 1999, 2002; Bry & Hoflack, 2004). The MOB and its biological compartments are subject to chronic pollution by some metals, especially Cd, representing a potential risk for shellfish cultivation (Pigeot et al., 2006; Strady et al., 2011). The latest estimates suggest that legal restrictions of oyster production in the MOB would result in a shortfall of between 50% and 70% of oysters on the market in the next years. Given that oyster is one of the top ten seafoods consumed in France, the economic consequences would be catastrophic for this region.

The Gironde Estuary, located ~30 km southward of the MOB, is affected by historic metal (e.g. Cd, Zn, Hg, Ag; Blanc et al., 1999; Schäfer et al., 2006; Castelle et al., 2009; Larrose et al., 2010; Lanceleur et al., 2011) contamination due to former Zn ore treatment in the industrial Decazeville basin, that was stopped after a major pollution accident in 1986. In this watershed drained by the Riou Mort River, anthropogenic contributions to particulate element fluxes were estimated to ~90-95% for Cd, Zn and Hg (Coynel et al., 2009). Despite decreasing Cd emissions in the Decazeville area due to ongoing remediation efforts since the early 1990s, the Lot-Garonne River system still contributes up to 80% to the annual Cd gross uxes into the Gironde Estuary (Schäfer et al., 2002; Audry et al., 2004). Additionally, intensive agriculture and ongoing urbanization also considerably contribute to metal (e.g. Zn, Cu, Ag) gross fluxes into the Gironde Estuary (e.g. Masson et al., 2006; Lanceleur et al., 2011). In contrast to the well-studied Garonne-Gironde system, the Charente fluvial-

Spatial Cadmium Distribution in the Charente Watershed and

in this section are the Ne and the Seugne Rivers.

on the Trezence River, the main tributary of the Boutonne River.

activities and practices (EPTB-Charente, 2007; Vernier et al., 2010).

situation is representative of a moderate to a high hydrological situation.

System.

**3. Material and methods 3.1 Sampling campaign** 

2009).

Potential Risk Assessment for the Marennes Oleron Bay (Southwest France) 23

 The downstream Charente River system is located between Angouleme and Saintes, and represented by Quaternary formations. The main tributaries of the Charente River

 The Charente Estuary, downstream of Saintes, is located in areas where sedimentary rocks and limestone prevail. Two dams have been set up within the estuarine reaches submitted to tidal influence: one at Saint Savinien on the Charente River and the second

The Charente watershed is considered predominantly as a rural sedimentary basin. Agriculture activities cover about 60% of this area and about 11% of the cultivated area is irrigated. However, 52% of the water bodies in this river system are at risk of failing the European Water Framework Directive objectives to achieve good ecological and chemical status, due to diffuse pollution (nitrates, turbidity, and pesticides) attributed to agricultural

The Charente watershed meteorology is characterized by the Atlantic Ocean disturbances. The mean annual water discharge of the Charente River is ~74 m3/s, corresponding to a specific discharge (average discharge/watershed area) of ~0.007 m3/s/km2, i.e. 3 times less than that of the adjacent Dordogne watershed (Regional Environment Agency- DIREN; BanqueHydro®; Schäfer et al., 2002). Two major factors contribute to this low specific discharge: on the one hand, relatively low supply from its major tributaries (the Tardoire and Bandiat Rivers) flowing over a karst formation and, on the other hand, intense agricultural irrigation throughout the basin. During our sampling campaign, the estimated Charente River water discharge at the watershed was ~100 m3/s (Charente River at Chaniers [CHA10; Figure 1] + Boutonne River; data from DIREN), implying that the studied

A sampling campaign was conducted from April 6 to April 8 2010. Strategic sites were selected by Geographical Information System (GIS, ArcView ®) for testing different environmental characteristics (e.g. geology, land-use) and evaluating their impacts on Cd concentrations. In total, 20 strategic sites were selected on the Charente River (n=10 sites; notified by CHA; Figure 1; Table 1) and its tributaries (n=10 sites; notified by a letter; Figure 1; Table 1) characterized by contrasting geology, industrial and agricultural activities. An additional site was chosen on a small drain near Riou Mort River (former mining area; "c", Figure 1) for collecting a stream sediment deposit. Note that this Riou Mort River in the Charente watershed is not identical with the well-studied Riou Mort River draining the polluted Decazeville basin, responsible for important historical polymetallic (mainly Cd, Zn, Cu, Pb, Hg, Ag) pollution in the Lot-Garonne river continuum (e.g. Blanc et al., 1999; Schäfer et al., 2002; Audry et al., 2004; Coynel et al.,

Mas-Chaban reservoir (176 ha; 14.2 Mm3) on the Moulde River, were built in 1989-1990. In this section, the Tardoire River is considered the main tributary of the Charente

estuarine system remains poorly studied in spite of its great hydrological influence on the MOB. The Charente River is the major river discharging directly into the MOB. During summer, 90% of the freshwater inputs into the Bay come from the Charente River (Ravail-Legrand, 1993), which drains an area of 10,549 km² dominated by farming (Bry & Hoflack, 2004). Only few studies have previously assessed the importance of the Charente Estuary to the overall metal contamination of the MOB (Gonzalez et al., 1991; Boutier et al., 2000; Dabrin, 2009). Recently, Dabrin (2009) showed that dissolved and particulate Cd concentrations the outlet of the Charente watershed, i.e. at the entry of the Charente Estuary were similar to those in the Garonne River and contributed up to 60% to total Cd inputs into the MOB, highlighting the need to precisely identify the origin(s).

In this context, the objective of this study is to (i) characterize the Cd content in water (<0.2 µm; dissolved phase) and in particles (SPM and stream sediments) exported by the Charente sub-watersheds; (ii) assess their level of contamination by comparison with world references and ecotoxicological indices and (iii) identify point sources and/or diffuse sources in the Charente watershed. This first assessment of the sub-watershed contributions to the fluvial Cd export is essential to the control and reduction of Cd contamination in oysters, i.e. to successful environmental management in this vulnerable region.

#### **2. Presentation of the study area**

The Charente watershed (surface area = 10,549 km²; ~500,000 inhabitants) is surrounded by the Massif Central to the East, the Paris sedimentary basin to the North, the Aquitaine sedimentary basin to the South and by the Armorican Massif to the Northwest (Figure 1). It is essentially composed of limestone formations dating from the Secondary: (i) in the North, the Jurassic formations are composed of large limestone beds in various facies and, (ii) in the South, the Cretaceous formations are formed by clay, sand, chalk and decalcification clays. The Primary formations crop out in the most upstream catchment areas of the Charente watershed, represented by plutonic and metamorphic rocks (BRGM, 2003).

Fig. 1. Location of sampling sites

The Charente watershed can be divided into three main domains (Figure 1):

 The upstream Charente watershed features metamorphic rocks to the East. Two large reservoir dams, the Lavaud reservoir (400 ha; 10 Mm3) on the Charente River and the Mas-Chaban reservoir (176 ha; 14.2 Mm3) on the Moulde River, were built in 1989-1990. In this section, the Tardoire River is considered the main tributary of the Charente System.


The Charente watershed is considered predominantly as a rural sedimentary basin. Agriculture activities cover about 60% of this area and about 11% of the cultivated area is irrigated. However, 52% of the water bodies in this river system are at risk of failing the European Water Framework Directive objectives to achieve good ecological and chemical status, due to diffuse pollution (nitrates, turbidity, and pesticides) attributed to agricultural activities and practices (EPTB-Charente, 2007; Vernier et al., 2010).

The Charente watershed meteorology is characterized by the Atlantic Ocean disturbances. The mean annual water discharge of the Charente River is ~74 m3/s, corresponding to a specific discharge (average discharge/watershed area) of ~0.007 m3/s/km2, i.e. 3 times less than that of the adjacent Dordogne watershed (Regional Environment Agency- DIREN; BanqueHydro®; Schäfer et al., 2002). Two major factors contribute to this low specific discharge: on the one hand, relatively low supply from its major tributaries (the Tardoire and Bandiat Rivers) flowing over a karst formation and, on the other hand, intense agricultural irrigation throughout the basin. During our sampling campaign, the estimated Charente River water discharge at the watershed was ~100 m3/s (Charente River at Chaniers [CHA10; Figure 1] + Boutonne River; data from DIREN), implying that the studied situation is representative of a moderate to a high hydrological situation.
