Supplementary information to

MMHg production and export from intertidal sediments to the water column of a tidal lagoon (Arcachon Bay, France).

S. Bouchet1*, D. Amouroux1, P. Rodriguez-Gonzalez1, E. Tessier1, M. Monperrus1, G Thouzeau2, J. Clavier2, E. Amice2, J. Deborde3, S. Bujan3, J. Grall4, and P. Anschutz3

1. Laboratoire de Chimie Analytique Bio-inorganique et Environnement, Institut Pluridisciplinaire de Recherche sur l’Environnement et les Matériaux, UMR 5254 CNRS - Université de Pau et des Pays de l'Adour, Hélioparc Pau Pyrénées, 2, av. P. Angot, 64053 Pau cedex 9, France

2. Laboratoire des Sciences de l’Environnement Marin, UMR 6539 CNRS/UBO/IRD, IUEM, Technopôle Brest-Iroise, 4 rue Dumont d’Urville, 29280 Plouzané, France

3. Laboratoire Environnements et Paléoenvironnements Océaniques et Continentaux (EPOC), UMR 5805 CNRS -Université de Bordeaux I, 33405 Talence, France

4. OSU IUEM, Technopôle Brest-Iroise, 4 rue Dumont d’Urville, 29280 Plouzané, France

* Corresponding author. Tel.: +33-5-59-40-77-56; fax: +33-5-59-40-77-81

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Materials and methods

Trace elements analyses

Concentrations of some trace elements were analyzed by ICP-MS (X7 II Thermo Elemental) by a conventional nebulization method and with standard addition methods to calculate their benthic fluxes, as for Hg species. The instrument was operated in the collision cell mode with a mixed gas (8 % H2 in a N5 grade He, Linde gas) to remove polyatomic interferences (Leonhard et al., 2002). Prior to analyses, the samples were precisely diluted ten times with ultra-pure water in order to decrease the salt content and minimize the matrix interferences. The results have been validated by the analyses of CASS-4 and NASS-5 (NRCC) certified marine waters (Pinel-Raffaitin et al., 2008).

Macrofaunal abundance and biomass in benthic chambers

In the field, macrofaunal samples were gently washed on a 1-mm sieve and preserved in 4% formaldehyde solution. At the laboratory, individuals were sorted, counted and identified to the species level under a dissecting or a compound microscope. For macrofauna biomass determination, samples were dried at 60°C for 48 h and the ash-free dry weight (AFDW) was calculated after 4h ignition at 450°C.

Ancillary data measurements

Sediment was freeze-dried and the weight loss was used to calculate water content. The dried solid was homogenized for solid-phase analysis. An ascorbate reagent was used to remove from the sediment the most reactive Fe (III) phases (Fe-asc), all Mn (III,IV) oxides and oxyhydroxides (Mn-asc), reducible by heterotrophic bacteria and associated phosphorus (P-asc; Kostka et Luther III, 1994; Anschutz et al., 1998, 2005; Deborde et al., 2007). Particulate organic carbon (C-org), total carbon (C-tot), and total sulphur (S-tot) were measured on freeze-dried samples by infrared spectroscopy using a LECO C-S 125. Particulate organic carbon was measured after removal of carbonates with 2 M HCl during 24 h from 50 mg of powdered sample. The precision of these analyses was ± 0.02 wt%. Dissolved Fe (II) was determined by the ferrozine method (Stookey, 1970) and dissolved Mn2+ by atomic absorption spectrometry. PO43- was measured with the spectrophotometric method described by Murphy and Riley (1970). The precision estimated from replicates was ±5% for Mn and P, and ±7% for Fe. DOC was measured with a high-temperature catalytic oxidation analyzer (Shimadzu TOC 5000). Dissolved sulfides were measured by a methylene blue method adapted from Cline (1969).


Table SI-1. Mean (± SD) benthic fluxes of oxygen and selected trace metals measured in the benthic chambers in March 2005, May 2006 and October 2007 in Arcachon Bay.



Fig. SI-1. Example of a typical sediment pore-water profile for dissolved inorganic phosphorus, ammonium, SCO2, Fe2+, Mn2+ and H2S, recorded at St.2 in May 2006.

Fig SI-2. Box-and-whisker plots representing the individual Hg species concentrations in the bottom waters (n = 45, lower and upper limits of the box represent the percentiles 25 and 75).

Fig SI-3. Box-and-whisker plots representing the distribution of the individual benthic fluxes values over the three periods studied (n = 39, 6 values discarded, lower and upper limits of the box represent the percentiles 25 and 75).

Fig Si-4. Relationships between IHg benthic fluxes and PO43- and Mn benthic fluxes for the three seasons considered.

References

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Anschutz P., Dedieu K., Desmazes F., Chaillou G. (2005). Solid speciation, oxidation state, and reactivity of manganese in marine sediments. Chem. Geol. 281:265-279

Cline (1969). Spectrophotometric determination of hydrogen sulfide in natural waters. Limnol. Oceanogr. 14:454-458

Deborde, J., Anschutz, P., Chaillou, G., Etcheber, H., Commarieu, M.V., Lecroart, P., Abril, G. (2007). The dynamics of phosphorus in turbid estuarine systems: Example of the Gironde estuary (France). Limnol. Oceanogr. 52:862-872.

Kostka, J.E., Luther III, G.W. (1994). Partitioning ans speciation of solid-phase iron in salt-marsh sediments. Geochim. Cosmochim. Acta 58:1701-1710.

Leonhard, P., Pepelnik, R., Prange, A., Yamada, N., Yamada, T. (2002). Analysis of diluted sea-water at the ng L-1 level using an ICP-MS with an octopole reaction cell. J. Anal. At. Spectrom. 17:189-196.

Murphy, J.; Riley, J. P. (1962). A modified single solution method for the determination of phosphate in natural waters. Anal. Chim. Acta, 27:31-36.

Pinel-Raffaitin, P., Barats, A., Bouchet, S., Bridou, R., Rodriguez-Gonzalez, P., Tessier, E., Monperrus, M., Bareille, G., Amouroux, D. (2008). Direct analysis of trace elements in estuarine and coastal seawater from the Bay of Biscay by Collision Cell –Quadrupole ICPMS, Proceedings of the XI International Symposium on Oceanography of the Bay of Biscay. San Sebastian, Spain, 2008 April 2-4