Anthropogenic components of heavy metal (Cd, Zn, Cu, Pb) budgets in the Lot-Garonne fluvial system (France)

Abstract Heavy metal (Zn, Cd, Cu and Pb) mass balances in the Lot-Garonne fluvial system have been established for 1999 and 2000. The mean annual discharges of these years are close to the mean discharge of the previous decade. The estimated annual dissolved and particulate fluxes in this model watershed integrate daily input from diffuse and point sources, diffusive fluxes at the water/sediment interface, changes in the dissolved-particulate partition and changes in sediment stock. Cadmium, Zn, Cu and Pb entering the Gironde estuary via the Garonne River (11–14 t a−1 of Cd; 1330–1450 t a−1 of Zn; 126–214 t a−1 of Cu and 127–155 t a−1 of Pb) are mainly transported in the particulate phase and the major part (i.e. ∼74 to 96% for Cd, ∼60% for Zn, ∼50 to 60% for Cu and ∼80% for Pb) is transported by the Lot River. The main anthropogenic heavy metal point source is located in a small upstream watershed (Riou-Mort River) accounting for at least 47% (Cd), ∼20% (Zn), ∼4% (Cu) and ∼7 to 9% (Pb) of the total heavy metal inputs into the Garonne River, although it contributes only 1% of the discharge. Mass balances for 1999 suggest that under mean annual hydrologic conditions on the basin scale, the heavy metal budget of the Lot-Garonne fluvial system is balanced and that the stocks of Cd [200 t; Environ. Tech. 16 (1995) 1145] and Zn in the Lot River sediment are constant under mean discharge conditions. Heavy metal input by molecular diffusion at the sediment surface represents an important component of dissolved metal inputs into the system (e.g. 30% for Cu). Except for Cu, these dissolved inputs are totally removed from solution by SPM. Based on the generally constant Zn/Cd (∼50) concentration ratio in sediment cores from the polluted Lot River reaches and the sediment stock of Cd [200 t; Environ. Tech. 16 (1995) 1145], the present day Zn stock in the Lot River sediments has been estimated at about 10,000 t. In addition to the mobilization of river-bed sediment and associated heavy metals by intense floods, local human activities, including river-bed dredging, may strongly modify the heavy metal budget of the river system. In 2000, the dredging-related remobilization of polluted Lot River sediment released 2–6 t Cd. This additional Cd point source was estimated to account for 15–43% of the gross inputs into the Gironde Estuary.

[1]  J. Jouanneau,et al.  Cadmium in the gironde fluvioestuarine system: Behaviour and flow , 1990 .

[2]  D. Walling,et al.  Estimating the discharge of contaminants to coastal waters by rivers: Some cautionary comments , 1985 .

[3]  J. Edmond,et al.  Chemical dynamics of the Changjiang estuary , 1985 .

[4]  S. Simpson,et al.  Effect of Short-Term Resuspension Events on Trace Metal Speciation in Polluted Anoxic Sediments , 1998 .

[5]  E. Boyle,et al.  Trace Elements in the Mississippi River Delta Outflow Region: Behavior at High Discharge , 1991 .

[6]  G. Blanc,et al.  Relationship between ore deposits in river catchments and geochemistry of suspended particulate matter from six rivers in southwest France. , 2002, The Science of the total environment.

[7]  Abraham Lerman,et al.  Geochemical Processes: Water and Sediment Environments , 1979 .

[8]  F. Elbaz-Poulichet,et al.  Preliminary assessment of the distributions of some trace elements (As, Cd, Cu, Fe, Ni, Pb and Zn) in a pristine aquatic environment: The Lena River estuary (Russia) , 1993 .

[9]  R. Glud,et al.  In situ study of bromide tracer and oxygen flux in coastal sediments , 1999 .

[10]  D. Loring,et al.  Manual for the geochemical analyses of marine sediments and suspended particulate matter , 1992 .

[11]  J. Trefry The Transport of Heavy Metals by the Mississippi River and Their Fate in the Gulf of Mexico , 1977 .

[12]  A. Schmidt,et al.  Contaminants in sediments: remobilisation and demobilisation. , 2001, The Science of the total environment.

[13]  M. Meybeck,et al.  Comportements des contaminants en trace dissous et particulaires (As, Cd, Cu, Hg, Pb, Zn) dans la Seine , 1995 .

[14]  P. Kelderman,et al.  Heavy metal contents in the Delft canal sediments and suspended solids of the River Rhine: multivariate analysis for source tracing. , 2001, Chemosphere.

[15]  J. Trefry,et al.  A Decline in Lead Transport by the Mississippi River , 1985, Science.

[16]  B. V. Eck,et al.  Geochemistry of dissolved trace metals (cadmium, copper, zinc) in the Scheldt estuary, southwestern Netherlands: Impact of seasonal variability , 1997 .

[17]  D. Claisse Chemical contamination of French coasts: The Results of a Ten Years Mussel Watch , 1989 .

[18]  D. Walling,et al.  Load estimation methodologies for British rivers and their relevance to the LOIS RACS(R) programme , 1997 .

[19]  C. Latouche,et al.  Pollution en Cadmium Dans Les Sédiments du Lot (France) et Calcul du Stock de Polluant Cadmium Pollution in Sediments of the Lot River (France). Estimate of the Mass of Cadmium , 1995 .

[20]  R. Gibbs Transport phases of transition metals in the Amazon and Yukon Rivers , 1977 .

[21]  R. Raiswell,et al.  Solid phase associations, oceanic fluxes and the anthropogenic perturbation of transition metals in world river particulates , 2000 .

[22]  Li Yuan-hui,et al.  Diffusion of ions in sea water and in deep-sea sediments , 1974 .

[23]  M. Fonton Provence-Alpes-Côte-d'Azur , 1976 .

[24]  G. Wattayakorn,et al.  Trace metal transport in a tropical estuary , 1988 .

[25]  F. Morel,et al.  Geochemistry of trace metals in the Gironde estuary , 1997 .

[26]  P. Lazure,et al.  Influence of the Gironde estuary outputs on cadmium concentrations in the waters: consequences on the Marennes-Oléron bay (France) , 2000 .

[27]  J. M. Martín,et al.  Distribution and behaviour of arsenic in the Huang He (yellow river) estuary and Bohai sea , 1988 .

[28]  E. Boyle,et al.  The chemical mass balance of the amazon plume—II. Copper, nickel, and cadmium , 1982 .

[29]  F. Elbaz-Poulichet,et al.  The Conservative Behaviour of Trace Metals (Cd, Cu, Ni and Pb) and As in the Surface Plume of Stratified Estuaries: Example of the Rh ône River (France) , 1996 .

[30]  G. Chaillou,et al.  The distribution of Mo, U, and Cd in relation to major redox species in muddy sediments of the Bay of Biscay , 2002 .

[31]  C. Latouche,et al.  Flux de matières en suspension et de cadmium dans le Lot , 1996 .

[32]  E. Millán,et al.  Chapter 12 - Contaminants in sediments , 2004 .

[33]  A. Robson,et al.  Major, minor, trace element and suspended sediment variations in the River Derwent , 1998 .

[34]  J. Jouanneau,et al.  Comparison of the different methods for the recovery of suspended matter from estuarine waters: Deposition, filtration and centrifugation; Consequences for the determination of some heavy metals , 1980 .

[35]  H. Etcheber,et al.  Ten-year observation of the Gironde tributary fluvial system: fluxes of suspended matter, particulate organic carbon and cadmium , 2002 .

[36]  Robert A. Berner,et al.  Early Diagenesis: A Theoretical Approach , 1980 .