The biogeochemistry of mercury at the sediment water interface in the Thau lagoon. 1. Partition and
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Archimer, archive institutionnelle de l’Ifremer Estuarine, Coastal and Shelf Science http://www.ifremer.fr/docelec/ Volume 72, Issue 3, April 2007, Pages 472-484 doi:10.1016/j.ecss.2006.11.015 © 2006 Elsevier The biogeochemistry of mercury at the sediment water interface in the Thau lagoon. 1. Partition and speciation a a* b b aB. Muresan , D. Cossa , D. Jézéquel , F. Prévot , S. Kerbellec a Institut français de recherche pour l’exploitation durable de la mer (IFREMER), BP 21105, F.44311 Nantes Cedex 03, France b Laboratoire de Géochimie des Eaux (LGE), UMR CNRS 7047 - Université D. Diderot & IPGP – Case postale 7052, 4, Place Jussieu, F.75251 Paris Cedex 05, France *: Corresponding author : Email address : dcossa@ifremer.fr Abstract Solid sediment, pore and epibenthic waters were collected from the Thau lagoon (France) in order to study the post depositional partition and mobility of mercury and monomethylmercury in an organic rich sediment. Total Hg (HgT) and monomethymercury (MMHg) profiles were produced in both dissolved and solid phases. The distribution of HgT in the solid appeared to be related to the historical changes in the Hg inputs into the lagoon. HgT was in equilibrium between solid and solution in the sulfidic part of the cores, with a mean log Kd of 4.9 ± 0.2. The solid appeared to be a source of HgT for pore water in the upper oxic to suboxic parts of the cores. The MMHg represented a small fraction ...
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| Publié par | Nething |
| Nombre de lectures | 19 |
| Langue | English |
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Estuarine, Coastal and Shelf ScienceArchimer,archive institutionnelle de l’Ifremer Volume 72, Issue 3, April 2007, Pages 472-484f./rmerei.rfw/wwlec/doceht:/tp doi:10.1016/j.ecss.2006.11.015 © 2006 Elsevier
The biogeochemistry of mercury at the sediment water interface in the Thau lagoon. 1. Partition and speciation a B. Muresan , D. Cossaa*, D. Jézéquelb, F. Prévotb, S. Kerbelleca aInstitut français de recherche pour l’exploitation durable de la mer (IFREMER), BP 21105, F.44311 Nantes Cedex 03, France bLaboratoire de Géochimie des Eaux (LGE), UMR CNRS 7047 - Université D. Diderot & IPGP Case postale 7052, 4, Place Jussieu, F.75251 Paris Cedex 05, France *: Corresponding author : Email address : dcossa@ifremer.fr Abstract Solid sediment, pore and epibenthic waters were collected from the Thau lagoon (France) in order to study the post depositional partition and mobility of mercury and monomethylmercury in an organic rich sediment. Total Hg (HgT) and monomethymercury (MMHg) profiles were produced in both dissolved and solid phases. The distribution of HgT in the solid appeared to be related to the historical changes in the Hg inputs into the lagoon. HgT was in equilibrium between solid and solution in the sulfidic part of the cores, with a mean log Kd of 4.9±0.2. The solid appeared to be a source of HgT for pore water in the upper oxic to suboxic parts of the cores. The MMHg represented a small fraction of HgT: 3-15 % and 0.02-0.80%in the dissolved and in the solid phases respectively. Its distribution was characterized by a main peak in the superficial sediments, and another deeper in the core within the sulfide-accumulating zone. In addition, high dissolved MMHg concentrations and methylated percentage were found in the epibenthic water. Ascorbate (pH 8) dissolution of the sediments and analyses of the soluble fraction suggest that the amorphous oxyhydroxides played a major role in controlling total and methylmercury mobility throughout the sediment water interface. These features are discussed in term of sources, transfer and transformations. Diffusive fluxes of HgT and MMHg fmro-2m s1ediment to the water column for the warm period were estimated to be 40±15 and 4±2 pmol d-. velyectierps Keywords: Mercury; Methylmercury; Lagoon; Sediment; Partition; Fluxes
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1. Introduction The toxicological concern regarding the bioaccumulation of mercury in aquatic food chains, mainly as monomethylmercury (MMHg), has given rise to extensive surveys of Hg concentrations and speciation in coastal environments, including water, sediments and biota (e.g., Bloomet al., 2004). There now exists a plethora evidence that near-shore sediments are repository sites for natural and anthropogenic Hg and are a significant source of MMHg for the marine food web (e.g., Bloomet al., 1999; Cossa and Gobeil, 2000). As a matter of fact, sediments have long been recognized as the main location for microbial Hg methylation especially within the redox transition zone containing sulfate-reducing bacteria (SRB) [e.g., Jensen and Jernelov, 1969; Gilmouret al., 1992; Kinget al., 1999; Masonet al., 1999; Benoit et al., 2003]. Several studies have recently prompted significant progress in the understanding of the methylating potential of sedimentary environments. Firstly, total mercury in the solid (HgTP) can be considered as a proxy for the substratum for Hg methylation, given that it is positively correlated with MMHg in surface sediments (Benoitet al., 2003). Secondly, the MMHg concentration in the solid (MMHgP) is an indication of the relative methylation rate (Bloomet al., 1999; Gilmouret al., 1998). Thirdly, the sulfide concentration, through the speciation and bioavailability of various Hg-S complexes, is thought to be a major factor controlling the bacterial methylation of inorganic mercury (Craig and Moreton, 1986; Benoit et al., 1999, 2001). In the fourth place, physical and/or biological turbations have been shown to alter the thickness of the suboxic layer and subsequently the amplitude of the methylation potential (Benoitet al., in press; Hammerschmidt and Fitzgerald, 2004; Sunderlandet al., 2004). In short, the magnitude and the dynamics of the redox interface, and the processes that govern the availability of inorganic Hg for SRB in the suboxic zone are the key for understanding the methylation potential of a particular sedimentary environment. As a consequence, the bioavailability can be approached by speciation and partition measurements in a well-described redox system. In order to reach this goal, it is necessary to know the distribution of inorganic and methylated mercury species in the dissolved and the particulate phase of the sediment (Fe and Mn oxyhydroxides, Fe sulfides, particulate organic matter, etc.). The Thau lagoon on the Mediterranean French coast is a pertinent environment for studying element exchanges at the sediment water interface (SWI). Firstly, the water column is shallow, providing a relatively high sediment area to water volume ratio. The lagoon also has a tendency to eutrophication leading to sulfidic sediments, especially in its shellfish-
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farming zone. With its permanent riverine, karstic and anthropic inputs, the Thau lagoon may therefore behave as a significant reactor for mercury methylation towards oxic-anoxic interfaces. This paper introduces and appraises the distribution of HgT and MMHg in the solid phase and pore water of sediment cores collected in the Thau lagoon, in order to study the post depositional partition and mobility of mercury. In order to ensure the most favorable conditions for biotic methylation, the pore water study was performed during the productive periods (spring and summer). Additionally, the likelihood for Fe and Mn oxyhydroxides sequestration of HgT and MMHg in the superficial sediment was examined through pH 8 ascorbate extraction. Finally, the average molecular diffusion fluxes for total dissolved mercury (HgTD) and dissolved monomethylmercury (MMHgD) were calculated on the basis of the gradient at the SWI. 2. Material and methods 2.1 Sample collection All the samples were collected within an area of 10 m x 10 m around Station C5 in the Thau lagoon (43°25'990N; 3°39’656E, Fig. 1). Water column and sediments were sampled during the different seasons from December 2001 to June 2004 (Table 1). Coring for pore water investigations were collected in May 2003 and in June 2004. The May 2003 sampling campaign (MB-5) was mainly devoted to mercury and methylmercury partitions in the sediment, with special attention being paid to spatial variability: 4 cores (noted #1, #2, #3 and #4) were taken at a 1 m distance from each other. The first one was close to the culture table on which the oysters are farmed, last was 4 m away. The June 2004 sampling campaign (MB-6) focused on methylmercury affecting processes at the SWI and in the epibenthic waters. The ultra clean sampling techniques and analytical methods applied for water analyses are those presented and discussed in detail by Bloom (1989) and Cossaet al. (2002 and 2003). In short, water column samples were collected by pneumatic pumping (an all Teflon double bellow ASTI pump) using acid-cleaned Teflon coated tubing. Samples were stored in acid- clean Teflon (PFA) bottles. Sediments were collected by divers using Teflon or Plexiglas corers. Sectioning was performed in a glove box under nitrogen when pore waters had to be extracted; otherwise it was performed in air. The sulfide-accumulating zone (SAZ) was identified with sulfide sensitive sellotape, through the formation of a surface darkening Ti-S complex (Jézéquelet al., this issue). Interstitial waters were extracted immediately after
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sampling by centrifugation (4000 rpm, 20 min) and subsequent filtration of the supernatant (Millipore® 0.45LCR filters) in accordance with Gobeil and Cossa µm hydrophilic Teflon (1993). Samples of water overlying the sediments were kept by divers for further comparison with the pore water. All water samples were acidified with 1 % (v/v) Suprapur®HCl, double bagged and stored at +4°C in dark conditions until analyses were performed. In June 2004 (MB-6), poral and epibenthic waters were additionally collected through the use of dialysis devices also called classic peepers (Masonet al., 1998). Classic peepers are compartmented probes, which are implanted into the sediment by divers. Compartments (or cells) integrate dissolved species distribution over a 20 mm depth interval. Two porous membranes (Millipore® 0.2 µm PVDF) ensure the bilateral diffusion and partition of dissolved species from poral and/or bulk water to the immediate Plexiglas cell (cell thickness: 1 cm; sample volume: 10 mL). Prior toin situimplantation, cells were filled with spring water with low HgT concentration (< 1 pM, Cristalline®), peepers were put into a water-filled plastic bag and dissolved oxygen was removed by bubbling for 12 hours with purified (iodided charcoal trap) nitrogen. The peeper was retrieved from the sediment after 8 days of equilibration. Peeper transportation and pore water sampling were performed under a nitrogen atmosphere. Peeper water was drawn in clean Teflon Oak-Ridge tubes and subsequently acidified with 200 µL HCl (Suprapur®Two sediment cores were collected within 50 cm). distance on both sides of the peeper. These provided centimetric scale solid phase data on water content, porosity, loss on ignition (LOI), HgT, MMHg in Fe and Mn oxyhydroxides. Pore and epibenthic waters were filtrated at 0.45 µm, while the peeper dialyses were performed through a 0.22 µm membrane. Given that Hg species might be associated with particles sizing between 0.2 and 0.45 µm, a cross comparison was made of the results of the two different filtration techniques. The mean dissolved HgT concentrations in water collected near the sediment (5-10 cm above the SWI) were 15 ± 4 pM when using peepers and 12 ± 3 pM using a Teflon bottle handled by a diver. The former was filtered through 0.2 µm and the latter through 0.45 µm membrane. It appears that no significant difference exists whatever the cutting size chosen. Similar results were found in Lavaca Bay (Masonet al., 1998): filtering through a 0.1 µm filter did not remove more MMHg or total Hg than filtration through a 0.45 µm filter. 2.2 Sample analysis In the field measurements for pH (Unisense pH and reference electrode protected against sulfide contamination with a seawater junction and calibration was performed with
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NBS pH buffers) and total sulfides (colorimetric determination ofΣH2S concentrations by the methylene blue method, Spectroquant® Merck kit) were carried out from the classic 14779 peeper samples. Loss on ignition (LOI) was determined as a proxy for organic matter content by measuring the weight loss on lyophilized sediment after 24 hours at 450°C. Porosity was derived from pore water and total sediment volumes and calculated in accordance with Boudreau (1996, see below). All mercury species in water samples were detected by cold vapor atomic fluorescence spectrometry (AFS). Dissolved HgTD was determined in compliance with Bloom and Fitzgerald (1988), by the formation of volatile elemental Hg (released by SnCl2 after 30 minutes of acidic BrCl oxidation, and its reduction, preconcentration on a gold column). Dissolved “reactive mercury (HgRD), an easily reducible fraction, was obtained within 4 hours of sampling by direct reduction with SnCl2. An automatic atomic absorption spectrometer (AAS: AMA-254®, Altec Ltd.) was used for HgTP determinations in the solid phase of the sediments. This technique consists of a calcination of the freeze-dried samples under an oxygen gas stream in order to produce elemental mercury vapor and its subsequent amalgamation on a gold trap; mercury vapor then being measured by AAS (Cossaet alThe detection limits, defined as 3.3 times the., 2002). standard deviation of the blanks, were 0.1 pM and 0.035 nmol⋅g-1 the dissolved and for particulate mercury analyses respectively. The corresponding reproducibilities (the coefficient of variation in percentage of five replicate samples) were lower than 10%. The accuracy for HgT determinations in solids was regularly checked using the reference material (MESS-3) from the National Council of Canada as certified reference material (CRM). Monomethylmercury was determined using the method initially proposed by Bloom (1989) and modified by Liang and al. (1994). MMHg D acidified water was extracted by CH in2Cl2 and then transferred into 40 mL of Milli-Q water by evaporating the organic solvent. The aqueous solution was analyzed for MMHg by chromatography after ethylation and adsorption/desorption on a Tenax® column. For MMHg P a 3 hour acidic dissolution (HNO3 65%) of approximately 200 mg freeze-dried sediments took place before the procedure described previously. Detection limits were 0.05 pM and 0.005 pmol⋅g-1for respectively a 20 mL water and 200 mg solid sample. Precision was less than 10%for all analyses. Using the available reference material (IAEA-405), the accuracy of the method was estimated to be less than 5%with 91 ± 8 % recovery. This technique was adapted from Leermarkerset al. (2001) and the detailed procedure is given by Cossaet al. (2002 and 2003).
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The amorphous oxyhydroxides fraction of the sediment was extracted by partial dissolution using ascorbic acid/citric acid (1/2.5 w/w) at pH 8, according to Kostka and Luther (1994). Iron and manganese present in the pore water (FeD and MnD) and in the oxyhydroxides (FeOx and MnOx) were measured by flame atomic absorption spectrometry (Varian, SpectrAA 600). Total (HgTOx) and methylmercury (MMHgOx) in this fraction were also determined using the same methods as for HgTD and MMHg D. All the analyses except HgRDdeterminations were performed within 2 months of sampling at the IFREMERlaboratory of Nantes, France. 2.3 Modeling the diffusive fluxes MMHgD HgT andDwere estimated at the C5 benthic boundary layer fluxes diffusive (BBL) using Fick’s first law: ℑ=−(ϕ⋅Dw/θ²)⋅(∂C/∂x)BBL Whereℑis the flux of a solute with concentration C at the depth x,ϕis sediment porosity,θ is tortuosity, and Dw the molecular diffusion iscoefficient of the solute in seawater. Measuring porosity the tortuosity was approached using Boudreau’s formulation: o volume =pre waterθ² = 1−ln ² solid volume+pore water volume The Dwfor MMHg Das MMHgCl and HgTDas HgCl42-were determined coupling the linear regressions of the infinite-dilution diffusion for cations and anions against temperature (Boudreau, 1996) with the infinite-dilution diffusion for ion pairs (Applin and Lasaga, 1984). The expression was calculated for temperature salinity and pressure from an empirical equation developed by Kukulka (1987). The adjustment for pore water viscosity of normal seawater was small at no more than 7 % (Li and Gregory, 1974). The respective approximations for MMHg D and HgTD T at = 18°C, S = 35 and P = 2 bar were 1.84⋅10-5 and 8.65⋅10-6cm²⋅s-1. 3. The Thau lagoon: environmental settings The Thau lagoon is situated on the French Mediterranean coast and spans 70 km² from 43°20’ to 43°28’ North and 3°31’50 to 3°42’30 East. With a mean depth of 5 m the residence times of water varies from 1 to 5 months (Péna and Picot, 1991). The Thau lagoon is divided into three sectors: one can find the “Crique de l’angle to the northeast, the “Eaux
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blanches lagoon to the southeats and the main sector called “Grand Etang. The lagoon is connected to the Mediterranean Seavia navigable channels. Mean salinity is about 35 but 3 can vary with the season from 28 to 37 (Millet, 1989). The “La Vène and “le Pallas rivers are the principal freshwater inputs into the system. A karstic resurgence (“la Vise) is also located in the “Crique de l’angle area. Shellifsh breeding and tourism make the Thau basin an important place for studying the mobility of mercury and methylation processes within a lagoon environment. The investigation site (C5), northeast of “Grand Etang,is located inside the shellfish farming district (Fig. 1). The Thau lagoon trace metals distributions in sediments can be divided into 3 distinct areas (Péna and Picot, 1991): (i) the west side with low contamination, low organic matter (OM) content and low fine particulate fraction (<63 µm) levels, (ii) the central region (a sink for fine suspended particles) with moderate contamination levels, (iii) the north side with high trace metals concentrations, high organic carbon content and a high fine particulate fraction. Recent measurements have shown concentrations of organic carbon of up to 4.4 % at Station C5 (Mesnageet al., this issue). The C5 site (located in the northern area) underwent anthropogenic inputs of Cu, Cd and TBT (RNO, 1998 and 1999). Sediment in C5 displayed a high proportion (> 90 %) of the fraction below 63 µm over the fraction below 2 mm. These were essentially composed of detritic quartz, aragonite, calcite and clays (Péna and Picot, 1991). LOI profiles were homogenous towards the surface (within the first 45 mm) and decreased semi-exponentially with depth. Negative redox potentials (down to 415 mV) coupled to high OM concentrations and summer hypoxic events accounted for a degraded ecosystem with a low diversity index (Calvarioet al., 1989). The water column was sampled in order to characterize the mercury speciation at a preliminary stage of the project. Figure 2 shows the vertical profiles obtained in a winter (MB-1, December 2001) and a summer cruise (MB-3, August 2002). During the winter cruise, the water column was stratified with a thermocline between 5 and 7 m, whereas the water was more homogeneous during the summer cruise (MB-3) with a warmer layer between 1 and 3 m. Mercury speciation measurements were performed on unfiltered water samples collected every meter down to 50 cm from the bottom (Fig. 2). Total mercury concentrations varied from 2.9 to 5.5 pM in summer and 1.4 to 2.5 pM during the winter cruise. The vertical distributions did not show any relationship with the stratification; in addition, it is more likely that the distributions were governed by the suspended matter distribution (Fig. 2). In fact, the
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dissolved fraction for HgT varied between 34 and 58 %, in the water column during the summer 2002 cruise, with the highest proportion in the first four meters. The proportion of reactive mercury (HgR/HgT), composed mostly of inorganic and labile organic mercury complexes, varied between 12 and 67 %, with the highest level found in surface water in winter. It is worthwhile noting the dissolved gaseous mercury (DGM, consisting mainly of Hg0Concentrations were fairly homogeneous as far down) and MMHg vertical distributions. as 6 m, but there was a bulge in MMHg concentrations at 1 and 2 m with the peaks in HgT and HgR. More striking were the significant increases in concentrations approaching the bottom (Fig. 2). In short, the vertical structures of mercury species in the water column indicate that (i) a large proportion of mercury is associated with the particulate phase, especially during the productive period within the photic layer, and (ii) that the concentration increase in several species near the bottom reveals an effect of the benthic layer by particulate matter resuspension or/and by diffusive processes at the SWI. These preliminary results favor the choice of this particular environment (C5) for studying the mercury transformation and exchanges at the benthic layer. 4. Results 4.1 Sediment characterization The mean sedimentation rate at Station C5 was 0.25 cm a-1according to Schmidtet al. (this issue). The sediment received strong but irregular particulate organic carbon fluxes (up to 4.4 % according to Mesnageet al% in our own cores). All the., this issue and LOI up to 20 diagenetic series took place within the upper centimeters of the sediment. Chemical gradients were very sharp, generating relatively significant fluxes. Oxygen penetration depth never exceeds 1.5 mm in winter and was less than 1 mm in May 2003 (Dedieuet al., this volume). In addition, this can be virtually zero during a “malaigue crisis(the total anoxia of the water column). The reduction in Fe and Mn oxides took place just below this thin oxic layer (Metzgeret alto be less than 5 mm., this issue). Dissolved iron layers were thin enough during the sampling periods (May 2003, MB-5), June 2004 (MB-6), but can actually spread up to 5 cm below the SWI (winter and spring seasons). Below this suboxic layer (or anaerobic oxidant layer), the concentration of sulfate decreased and sulfides appeared around 3-4 cm below the SWI in May 2003 (Metzgeret al., this issue). 4.2 Mercury in the solid phase
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HgTPconcentration distributions showed a steady increase with a depth from 1.7 ± 0.3 nmol⋅g-1at the SWI to 2.3 ± 0.5 nmol⋅g-1130 mm below (Fig. 3). According to the dating by Schmidtet albottom of the cores (130-140 mm) is thought to shelter. (this issue), the sediment deposited 50 years ago. Distributions were even variable within the perimeter of collection (core #1, #3 and #4 collected in May 2003) and time of collection (cores taken in December 2001, August 2002 and May 2003). The concentration levels were several times higher (1.9 ± 0.3, 2.1 ± 0.2 and 2.0 ± 0.3 nmol⋅g-1MB-1, 3 and 5 respectively) than theduring accepted background values for unimpacted coastal sediments, usually lower than 0.5 nmol⋅g-1 (Cossaet al., 1990). The same pattern was observed for other analyzed metals, and interpreted as the result of contamination over the last 100 years, which has decreased in the last few decades (Elbaz, personal communication). In addition, the unusual negative correlation (r² = 0.52) between HgTPand LOI attests an anthropic signature. MMHg Pranged from 0.35 to 12.75 pmol⋅g-1(Fig. 4). Such levels were also found in sediments from the Seine estuary (Mikacet al., 1999), San Francisco Bay-Delta (Choeet al., 2004) or Long Island Sound (Hammerschmidt and Fitzgerald, 2004). Both the horizontal and vertical MMHg P patterns contrasted with those of HgT distributionP. Except for core #4, vertical distribution of MMHg Pstrong decreasing gradient within the first 30 mmdisplayed a (Fig. 4). The concentrations varied slightly or remained relatively constant further down the core. In addition, MMHg P presented an overall horizontal increasing pattern with profiles proximity to the ropes of the culture table which the oysters were attached to (from 1.2 ± 0.5 pmol⋅g-1 8 to ± 2 pmol⋅g-1average concentrations in each core were considered,). When the there was found to be a significant positive relationship between MMHgPand LOI (r² = 0.71). The fraction of HgTPas MMHg Pin marine and estuarine sediments is generally low (< 0.5%) (e.g., Bartlettet al., 1981, Benoitet alIn the Thau lagoon the ratios ranged from 0.02., 1998). to 0.80% averaging 0.24 %. The distribution of the methylated solid fraction was higher towards the SWI and decreased with depth. 4.3 Mercury in the dissolved phase 4.3.1 Sediment core data (MB-5, May 2003) Even if dissolved oxygen (Dedieuet al., this volume), manganese and iron (< 0.45 µm) profiles revealed a sharp lateral heterogeneity of the sediment within a small perimeter (< 1 m), general patterns can be described. The range of the oxygen penetration depths was less than 4 mm, and FeDpresence ranged from 10 to 70 mm in thickness, depending on the core, with concentrations between 10 and 200 µM (Fig. 5). Except for Core #1, the first centimeters
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below the SWI were mainly suboxic. In the deepest part of the cores, passing through the sulfide-accumulating zone (SAZ), iron was precipitated as sulfide even if low levels of dissolved FeS complex might have been present (Jézéquelet al., this volume). The HgTDconcentrations (15 to 85 pM) were found to vary widely from one core to the next (Fig. 6). Mean concentrations (30 ± 15 pM) were in the same order of magnitude as those reported for estuarine sediments (up to 50 pM) (Cossa and Gobeil, 2000; Sunderlandet alfor Core #1, the distributions of HgT., 2004). Except Ddisplayed a general trend of higher values close to the FeDmaximum (within the first 60 mm) or to the SAZ, which suggests a Hg mobilization associated with the solubilization of iron solid phases (oxides and sulfides). A slight increase in HgTDwas observed with depth (Fig.6) below 100 mm. Despite the high variability from one core to another, MMHg Din pore water showed a pronounced subsurface maximum, typically at 5-40 mm below the surface. The maximum concentrations of MMHg D in subsurface sediment varied from 0.5 to 2.5 pM and measured were consistent with MMHg Dfrom other similar environments (e.g., Choeet al., 2004). The proportion of HgT as MMHg in the dissolved phase (MMHg D/HgTD) in surface sediments (upper 40 mm) was found to be 3-15%. Core profiles exhibited another MMHg Dmaximum coincidental with or adjacent to the SAZ. Depending on the core, the MMHg Dpeak was 20-60 mm thick, with concentration maxima close to 1 pM (Fig. 6). As the oxygen penetration showed the redoxcline to be located within the first millimeters of the sediment (Dedieuet al., this volume), the lower MMHg D (below 30 mm) was clearly within anaerobic maximum conditions. 4.3.2 Peeper dialysis measurements (MB-6, June 2004) Peeper water displayed similar Hg distribution patterns as that obtained by pore water extraction in May 2003. High concentrations of HgTDand MMHg Dwere found 30 mm below the SWI (14 and 3.5 pM respectively, Fig. 7). Concentrations within the first 130 mm above the SWI (epibenthic water) were surprisingly high especially for MMHg D to 3.1 pM) (up compared to 0.03 to 0.09 pM measured in oxic water at 50 mm above the SWI in May 2003. The methylated fraction of the HgTD attained 40% sediments and 17 in% epibenthic in water. The peepers provided comparative total sulfide (ΣH2S) and pH distributions in pore and epibenthic water (Fig. 7). The pH profile covered 0.5 units from 7.5 (270 mm deep) to 8.0 (70 mm above the SWI). Just below the SWI the pH dropped by 0.23 with a gradient of -0.06
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unit⋅cm-1towards the interface and decreased slowly with depth. Pore water pH was higher excluding a drop in the deeper sediments (from 210 to 270 mm).ΣH2S concentrations varied from 0.02 mM at 10 mm above the SWI to 24.2 mM 270 mm below. PerceptibleΣH2S concentrations (> 10 µM) within epibenthic water suggested the occurrence of a hypoxic event in the water column. ΣH2S concentrations also showed a linear gradient with depth (r² = 0.99) within 210 first mm below the SWI. MMHg DandΣH2S were positively correlated in epibenthic water (r² = 0.79 up to 110 mm) but negatively bound in pore water (r² = 0.90 down to 150 mm) (Fig. 8). According to Benoitet al. (2003), the optima in methylation rate derive from the combination of the increase availability of Hg to the SRB coupled with a decreasing sulfate reduction rate. When plotted againstΣH2S, the dissolved methylated fraction gradient (δ(MMHg D/HgTD)/δ(position), a proxy ofin situ methylation) exhibited two well-defined optima: a maximum at 1.9 mM suggesting a production zone and a minimum at 11.9 mM suggesting a removal processes These two concentrations correspond to the expected depths (30 and 130 mm respectively) for “endogenic methylation and the precipitation of insoluble metacinnabar (HgS) or pyritization (e.g., Morse and Luther III, 1999). 4.4 Water-solid partitioning of mercury In May 2003 (MB-5), despite a high spatial variability (Fig. 6), the HgTDdistribution in pore water was characterized by two distinct patterns. In the deepest part of the cores, where iron is thought to precipitate as sulfide (Fig. 5), the distributions of HgTD HgT andP were parallel ([HgTD] = 14[HgTP] 8; r²= 0.53 and n=23). The logKdHgTbelow the SAZ were constant with depth (4.92±0.14). This suggests that an equilibrium between solid and dissolved phases dominates the HgT distribution in the presence of sulfide (Fig. 9). Conversely, in the upper parts (between 20 and 70 mm depending on the core), with iron in the dissolved phase, HgTDand HgTPdistributions were mirror images of each other ([HgTD] = - 55[HgTPdissolution / desorption and precipitation /]+130; r²=0.52 and n=15), reflecting adsorption processes out of equilibrium. The logKdMMHgshowed lower values than logKdHgT. Wide variations of the partition coefficients for MMHg (from 2.96 to 4.63) were observed near the SWI and SAZ, which also suggest a non steady-state situation (Fig. 9). The low concentrations of HgTDand MMHg Dat the SWI (Fig. 7) suggest a removal process, which we construed to be due to the scavenging of dissolved mercury species on the superficial oxyhydroxides. The results of the selective dissolution of this mineral phase on two cores collected during the June 2004 are shown in figure 10. They revealed a surface
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