Properties of fluorescent dissolved organic matter in the Gironde Estuary

The isolation, characterization and study of the properties of aquatic dissolved organic matter (DOM) still represent a challenge because of the heterogeneity, complexity and low concentration of organic material in natural waters. Based on its ability to interact with contaminants and thus to modify their transport and bioavailability, DOM is of interest for environmental purposes. The objective of this work was to better characterize DOM in the Gironde Estuary (southwestern France). The estuary represents an exchange zone between the continent and the Atlantic Ocean and conditions the transfer of organic and inorganic substances from the continental to the oceanic environment. Several samples were collected along the estuary during three cruises in 2002 and 2006. They were analysed using excitation–emission matrix (EEM) spectroscopy, a sensitive technique that allows direct analysis of water samples. Fluorescent DOM and dissolved organic carbon (DOC) did not behave conservatively in this estuarine system, i.e. the organic material did not undergo simple dilution from the upstream to the downstream part of the estuary. A seasonal variability in DOC content was pointed out, whereas few seasonal variations in DOM fluorescence were observed. DOM sources and processing in the estuary were further evaluated by determining two fluorescence indices – the humification index (HIX) and the index of recent autochthonous contribution (BIX). By applying these indices, the relative degree of humification (HIX) and autotrophic productivity (BIX) could be assessed. Based on the fluorescence and DOC results, the estuary was divided into three zones depending on salinity (S) and characterized by specific DOM: (i) A turbid zone of low salinity (S < 5) and high suspended particulate matter concentration with increase in the intensities of the α′ and α fluorophores, characteristic of humic-like compounds. (ii) A mid-estuarine zone (5 < S < 25) characterized by low autotrophic productivity and containing strongly degraded organic material, as shown by the low values of BIX and high values of HIX. (iii) A higher salinity area (S > 25) characterized by increased autotrophic productivity and a marked marine influence, and associated with high and low values of BIX and HIX, respectively. The HIX and BIX indices were shown as useful tools for readily defining and classifying DOM characteristics in estuarine waters.     

Long-Term Changes in Population Dynamics of the Shrimp Palaemon longirostris in the Gironde Estuary

Spanning 20?years (1979?C2007), this study is the longest time series pertaining to the resident shrimp species Palaemon longirostris in a European estuary. Data from monthly faunal surveys undertaken across the middle part of the Gironde estuary from April 1979 along with data from a statistical analysis of the commercial catches throughout the entire estuary and river were considered in order to explore their inter and intra-annual variability and long-term trends. Long-term densities series as well as environmental series (salinity, discharge, temperature and NAO) were decomposed and the effects of environmental variables were also examined using statistical models (GAMs). This revealed important spatio-temporal variability and a significant overall decrease in abundance of this species in the Gironde estuary since the beginning of the 1980s. This long-term decrease in abundance corresponded significantly to long-term decreases in both discharge and the NAO index, as well a long-term increase in temperature and salinity in the middle part of the estuary. However, models showed that environmental factors explained only a small part of the variability. The upstream shift of the population highlighted in this study, probably due to the intrusion of marine waters into the middle section of the estuary, may also have contributed to its decrease in abundance. Inter-annual variability of densities was also significantly linked with inter-annual fecundity fluctuations, and a significant decrease in both mean female size and fecundity was shown for preserved samples from 1992. Moreover, the breeding period has been temporally stretched out and began earlier in more recent years, potentially due to the increase in spring temperature.     

Dynamics of coarse particulate matter in the turbidity maximum zone of the Gironde Estuary

There is a lack of studies devoted to coarse particulate matter (CPM) in estuaries, although this fraction can disturb activities that filter large volumes of water, such as industrial or fishery activities. In the macrotidal and highly-turbid Gironde Estuary, a monthly sampling of CPM was performed in 2011 and 2013 at two stations in the Turbidity Maximum Zone (TMZ) to understand its seasonal, tidal and hydrological dynamics. Regardless of the season and station, low quantities of CPM (few g m⁻³) were observed in comparison with suspended particulate matter (several 10³ g m⁻³). The highest concentrations were consistently recorded in bottom waters and at the upstream station. Whereas there is no clear link between the CPM present in the column water and spring or neap tides, an increase in the CPM size has been identified at the two stations after a flood event, fact potentially critical regarding filtering functioning of estuarine activities.     

Assessing the current state of the Gironde Estuary by mapping priority contaminant distribution and risk potential in surface sediment

Based on high spatial resolution monitoring, the first spatial distribution maps for the eight trace elements identified as priority contaminants in aquatic systems (i.e. As, Cd, Cr, Cu, Hg, Ni, Pb and Zn) in surface sediments of the Gironde Estuary (SW France) are presented. This large European fluvial–estuarine system is known for important historical multi-element (mainly Cd, Zn, Cu and Pb) pollution by former mining and mineral processing activation in the Riou-Mort watershed located 350 km upstream the estuary. As a consequence, oyster production in the estuary is prohibited, and Cd concentrations in oysters from the Marennes-Oléron area are close to consumption thresholds. Surface sediment samples were analysed for grain size, particulate organic C and trace element concentrations. Determination of trace elements was carried out by ICP-MS for As, Cd, Cr, Cu, Ni, Pb, Th and Zn, and by CV-AAS for Hg. Total and potentially released trace element stocks in the surface sediment were evaluated by using concentrations in the estuary and in selected sediment core. Assuming that sediment resuspension affects mainly the uppermost sediment layer, the total trace element stocks in the studied 0–10 cm depth range may represent the equivalent of one (Cd) to eight (As, Cr) times the annual fluvial trace element inputs into the estuary. Comparing total trace element concentrations in surface sediment with: (i) data on the regional geochemical baseline to evaluate the potentially remobilised fraction and (ii) the potentially bioavailable fraction aimed at establishing a first spatially resolved risk assessment of the trace element “cocktail” present in these sediments at the estuary scale. After correction for grain size effects by Th normalisation, potentially highly toxic metals such as Cd and Hg showed the highest enrichment factors. From ecotoxicological indices, areas were identified and quantified where trace element levels and mobility may bear a risk to benthic organisms. The GIS-based spatial distribution of ecotoxicological indices for the trace element “cocktail” suggests that ∼95% of the surface sediment are ‘Low–Medium’-priority zones, highlighting the need for further impact studies. The produced maps of trace element distributions and associated risk potentials are likely to be a useful tool to authorities in charge of sustainable estuarine management, e.g. for the optimisation of dredging activities or development of the estuarine infrastructure.     

Leaf litter degradation in highly turbid transitional waters: preliminary results from litter-bag experiments in the Gironde Estuary

The rates of decomposition of oak (Quercus robur) leaves have been examined using litter bags in a very high turbidity macrotidal estuary, the Gironde Estuary (S.W. France). The first experiments show a marked decrease in the decomposition rate of oak leaves at the water-sediment interface (mud-contact: anoxic conditions, reduced physical fragmentation) in comparison to the water column. The results point out the impact of hydrodynamic conditions on leaf litter degradation in such fluvio-estuarine systems. Regarding the aquatic-terrestrial linkage, our observations suggest direct changes in leaf decomposition kinetics and then, a potential delay on the recycling and transport processes of coarse particulate organic matter, especially in a context of modification of the natural water flow, due to global and land use changes.     

Behavior of arsenic and antimony in the surface freshwater reaches of a highly turbid estuary, the Gironde Estuary, France

This study reports on the behavior of two redox-sensitive elements, As and Sb, along the turbidity gradient in the freshwater reaches of the turbid Gironde Estuary. During a 17-month survey, surface water and suspended particulate matter (SPM) were sampled monthly at six sites representing both fluvial branches of the Gironde Estuary. Additionally, two longitudinal high resolution profiles were sampled along the fluvial estuary of the Garonne Branch during two contrasted seasons, i.e. with and without the presence of the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of dissolved (<0.2 μm; <0.02 μm) and particulate As, Sb and Fe were measured and combined with SPM data to understand metalloid behavior in the estuarine freshwater turbidity gradient.At the two main fluvial entries of the Gironde Estuary, dissolved As and Sb concentrations showed strong (by a factor of 2–4) seasonal variations, that were only partly controlled by discharge-related dilution. Seasonal addition of dissolved As and Sb was attributed to the degradation of particulate As and Sb carrier phases in bottom sediment and/or in the adjacent aquifers, rather than release from SPM. In the surface freshwater reaches of the Gironde Estuary, Sb behaved conservatively under all hydrological conditions. In contrast, As was strongly reactive in the presence of the MTZ, with opposite behaviors in the two fluvial branches of the estuary: in the Garonne Branch As was removed from the dissolved phase, whereas in the Dordogne Branch As was added. Redistribution of As between the dissolved and the particulate phases along the turbidity gradient in estuarine freshwater only affected the <0.02 μm fraction, as the 0.02–0.2 μm fraction remained constant (300 ng L⁻¹ in September 2005). Accordingly, As removal seemed to be decoupled from concomitant “colloidal” (0.02–0.2 μm) Fe flocculation in the turbidity gradient. The contrasting behavior of dissolved As in the fluvial estuaries of the Garonne and Dordogne Branches was attributed to sorption processes during equilibration of river-borne dissolved As with estuarine SPM forming the MTZ. This equilibrium, described by a distinct distribution coefficient K_d(As)  11,000 L kg⁻¹ in the MTZ, resulted in either As release (desorption; Dordogne Branch) or removal (adsorption; Garonne Branch) in the respective fluvial estuaries. A mixing experiment under controlled laboratory conditions tended to support that equilibration between the dissolved phase and MTZ particles may induce both As release and removal in the estuarine freshwater reaches, with As distribution evolving towards a distinct K_d value for increasing SPM concentrations. The long-term survey allowed estimating annual (2004) dissolved fluxes of As and, for the first time Sb, at the main fluvial entries of the Gironde Estuary at 30.7 t a⁻¹ and 3.2 t a⁻¹ (Garonne River) and at 8.0 t a⁻¹ and 2.3 t a⁻¹ (Dordogne River), respectively.     

Lignin geochemistry of sediments from the Narragansett Bay Estuary

Cupric oxide oxidation has been employed to characterize the lignin geochemistry of Narragansett Bay sediments. Lignin concentrations throughout the estuary are low when expressed on a carbon-normalized basis, but can be characterized as enriched when expressed on a mass-normalized basis. This implies substantial dilution of the sedimentary lignin by inputs of lignin-poor carbon. Lignin concentrations do not correlate with the ¹³C isotopic composition of the sedimentary organic matter. These results are consistent with a sediment lignin component consisting of varying amounts of vascular plant debris and lignin-depleted organic matter, the latter originating from both marine (planktonic) and terrestrial (uncharacterized) sources. Compositional plots of lignin-derived phenols show that sediments in the upper estuary are influenced to a greater extent by gymnosperm lignin sources than those in the mid-and lower estuary. Given the extent to which the upper estuary is affected by pollution sources, inputs from anthropogenic discharges are the most likely cause of these compositional differences. However, an evaluation of processed paper products as an “anthropogenic” lignin source indicates that the lignin content of these materials is insufficient to account for the levels found in the sediments. Subsurface lignin compositions at an upper estuary site reveal that lignin originating from the inferred anthropogenic sources disappears at a depth shallower than that which would be expected based on the distribution of other trace organic pollutants (hydrocarbons and several synthetic organic compounds). We speculate that differences in either the depositional history or the degree of preservation of these two compound classes are responsible for the observed trends.     

Organic matter distribution in the modern sediments of the Pearl River Estuary

We determined biomarker concentrations and distributions for surface sediments from 54 sites in the Pearl River Estuary, China. We focus on a suite of four biomarker-based indicators for relative terrestrial to marine organic matter (OM) source: the branched-isoprenoid tetraether (BIT) index, the ratio of high/low molecular weight n-alcohols [(ΣC_26–34/(ΣC₁₆₊₁₈ + ΣC_26–34)], an analogous ratio for n-fatty acids and the ΣC₂₉-steroids/(ΣC₂₉-steroids + brassicasterol) ratio. All four exhibit the same terrestrial to marine transition seen in previous bulk δ¹³C studies, but with an abrupt decrease in the relative terrestrial contribution across the delta front to pro-delta transition. Concentrations of terrestrially-derived biomarkers show no systematic decrease across the transition. Instead, the decrease in the proportion of terrestrial OM is due to a decrease in the sedimentation rate and associated terrestrial OM burial across the delta toe. This suggests that diagenetic controls on the fate of terrestrial OM, such as increased biodegradation where sedimentation rate is low, are subordinate to sedimentological processes. Biomarker-derived temperature values are cooler than expected for the lower Pearl River catchment, suggesting that the dominant component of the terrestrial OM is derived from the cooler upland regions of the catchment. The dominance of input from more distal terrain with greater topographic relief is evidence for the importance of geomorphological control on terrigenous OM transport. Collectively, the results demonstrate the importance of sedimentological processes in the supply, deposition and transport of terrestrial OM.     

长江口崇明东滩沉积物地球化学记录及其环境意义

利用2002年在崇明东滩采得的CDS、CDM和CDN三个典型区域沉积物剖面样品,测定了其中的有机碳、活性铁、总磷以及粒度等特征参数,分析了地球化学元素的分布变化特征并对其沉积环境的变化进行了探讨。结果表明崇明东滩沉积物中有机碳的含量较大(0．3％～1．07％),垂向分布上,表层／亚表层含量高且变化复杂,中下层有机碳含量逐渐变小。Fe3 在整个研究区域均是从表层向下逐渐递减的,Fe2 含量逐渐增加。从实验结果判断,所研究区域沉积环境上层以氧化环境为主,呈弱氧化型,中下层以还原环境为主。总磷含量呈现自上而下减少的变化,CDS表现为波浪形变化。分析发现潮滩沉积物各地球化学元素之间不仅相互作用,并且受到沉积物颗粒大小和水动力、物源输入、物理扰动等因素的影响。崇明东滩沉积物氧化还原界面与中、高潮滩划分界大致相当。     

Phosphorus speciation and availability in intertidal sediments of the Yangtze Estuary,China

In order to better understand P cycling and bioavailability in the intertidal system of the Yangtze Estuary, both surface (0–5 cm) and core (30 cm long) sediments were collected and sequentially extracted to analyze the solid-phase reservoirs of sedimentary P: loosely sorbed P; Fe-bound P; authigenic P; detrital P; and organic P. The total sedimentary P in surface and core sediments ranged from 14.58–36.81 μmol g⁻¹ and 17.11–24.55 μmol g⁻¹, respectively, and was dominated by inorganic P. The average percentage of each fraction of P in surface sediments followed the sequence: detrital P (54.9%) > Fe-bound P (23.7%) > organic P (14.3%) > authigenic P (6.3%) > loosely sorbed P (0.8%), whereas in core sediments it followed the sequence: detrital P (61.7%) > Fe-bound P (17.0%) > authigenic P (13.1%) > organic P (7.5%) > loosely sorbed P (0.7%). Post-depositional reorganization of P was observed in both surface and core sediments, converting organic P and Fe-bound P to authigenic P. The accumulation rates and burial efficiencies of the total P in the intertidal area ranged from 118.70–904.98 μmol cm⁻² a⁻¹ and 80.29–88.11%, respectively. High burial efficiency of the total P is likely related to the high percentage of detrital P and the high sediment accumulation rate. In addition, the bioavailable P represented a significant proportion of the sedimentary P pool, which on average accounted for 37.4% and 25.1% of the total P in surface and core sediments, respectively. This result indicates that the tidal sediment is a potential internal source of P for this P-limiting estuarine ecosystem.     

Vertical accretion rates and heavy metal chronologies in wetland sediments of the Tijuana Estuary

This study represents the first report on sediment accretion rates using¹³⁷Cs dating for a southern California salt marsh. Vertical accretion rates ranged from 0.7 to 1.2 cm yr⁻¹, which is at the high end of sediment accretion values for coastal wetlands. This has lead to increases in elevation within the estuary from 18 to 35 cm over the last 35 years. Depth profiles of metal concentrations were converted to time-based profiles using vertical accretion rates. Chronologies for most cores indicate a consistent peak in sediment lead (Pb) concentrations in the early to mid 1980s, corresponding to the historic decline in Pb use, which was completed in the U.S. by the early 1980s, but not begun in Mexico until 1991. Sediment Pb levels ranged from about 6–56 μg g⁻¹. Other metals did not show any consistent trends in sediment chronology, except for a single core from a mid-marsh site (east-mid 2), which showed a 2–3-fold increase in levels of Cu, Ni, and Zn during the past two decades. Sediment levels of copper (Cu), nickel (Ni), and zinc (Zn) ranged from 6–34 μg g⁻¹, 11–27 μg g⁻¹, and 42–122 μg g⁻¹, respectively. Despite rapid industrial development of the watershed, a comparison of the sediment metal concentrations in the Tijuana Estuary to other anthropogenically-impacted estuaries in the United States and Europe, shows that metal levels in sediments of the north arm of the estuary are relatively low.     

Silver fluxes to the Gironde Estuary - Eleven years (1999-2009) of monitoring at the watershed scale

Although Ag has long been recognized as highly toxic to aquatic organisms and as an efficient tracer of urban wastewater inputs, there are very few data available on Ag levels and fluxes in rivers and estuaries. Due to anomalously high Ag concentrations in oysters from the estuary mouth, dissolved (Ag_D) and particulate Ag (Ag_P) concentrations in rivers of the Gironde Estuary watershed were studied. Using daily discharge, Suspended particulate matter (SPM) data and monthly measured Ag_D and Ag_P, the respective fluxes were estimated at the three main entries of the Gironde Estuary and at selected key sites at the outlets of different sub-watersheds for multiple years of the past decade. Dissolved and particulate Ag concentrations were 0.5 ng/L (detection limit) to 5.7 ng/L and 0.13-13.9 mg/kg in all rivers, except for the Riou-Mort River (up to 1260 ng/L and 261 mg/kg) that has been heavily polluted by former Zn ore treatment and remaining waste tailings. At all sites Ag transport mainly (73-100%) occurred in the particulate phase, i.e. strongly depended on hydrological parameters. Comparing Th-normalised (i.e. grain size independent) Ag_P levels at the different sites including one remote site showed that the regional background is best described by Ag_P/Th_P = 0.026. The anthropogenic components in Ag_P levels and fluxes ranged from 24% to 90% at all sites, except for the Riou-Mort River (81-99%). Although this former ore treatment site still is an evident Ag source to the Lot-Garonne fluvial-estuarine system, its contribution to Ag fluxes at the main entry of the Gironde Estuary (i.e. 0.33-2.44 t/a at the La Reole site) is <11%. This clearly suggests that other sources such as rock weathering and erosion (0.057-0.817 t/a), urban wastewater inputs (0.042-0.057 t/a) and cloud-seeding (0.030-0.063 t/a) contribute the major parts of the fluvial Ag budget in this watershed. The estimated anthropogenic surface- and population-specific Ag fluxes in the studied system were 1.14-682 g/km²/a and 0.028-6.05 g/person/a, respectively. The results obtained suggest that the Gironde fluvial-estuarine system is contaminated by Ag inputs from various sources, but further work is necessary to (i) identify and quantify the major sources and (ii) produce comparable data for other systems, which would be useful for the evaluation of Ag contamination at a larger scale.     

Evolution of heavy-metal profiles in river Weser Estuary sediments,Germany

Studies of heavy metal concentrations in porewaters and in sediments from the Weser Estuary, Germany, indicate that the depth distribution of Mn, Cd, and Cu in the solid phase is predominantly influenced by the subsurface redox regime, while Ni shows only moderate alteration. Based on solid-phase heavy metal data from eight locations in the study area, linear regressions of Fe, Mn, Cu, Ni, and Cd on Al allowed differences between the initial metal concentration and the concentration preserved in the sediments to be predicted. We calculate that, due to early diagenetic processes, Mn is enriched to 145 percent, while Cu and Cd are depleted to 71 percent and 46 percent, respectively, of the initial metal concentration in the near-surface sediment. Maximum depletion of Cd (84 percent), Cu (68 percent), Mn (54 percent), and Ni (24 percent) concentrations in the sediment, observed at a restricted area downcore, indicate the importance of post-depositional processes to metal preservation in the sediment. Without knowledge of the quantitative effects of diagenetic reactions on the preservation of metal concentrations in sediments, the depth distribution of metals in sediment cores may be misinterpreted as the effect of human activities.     

Ammonium adsorption by tidal flat surface sediments from the Yangtze Estuary

Ammonium adsorption by sediments plays an important role in the cycle of nitrogen in the estuarine tidal flat ecosystem. Ammonium adsorption on tidal flat sediments from the Yangtze estuary was studied using the simulation experiment. The findings indicated that there was linear adsorption by the tidal flat sediments for the lower ammonium concentration (<10 mM) in the overlying waters. The adsorption coefficient of ammonium in the study area ranged from 3.81 to 9.00, and had a significant positive correlation with total organic carbon (r = 0.779, = 0.02284 , n=8), reflecting that organic matter might be one of the main factors controlling the behavior of ammonium adsorption. It also showed that salinity had a pronounced effect on ammonium adsorption, and that salinity affected the distribution of ammonium between the sediments and waters. The amount of ammonium adsorption on sediments gradually decreased with the increasing salinity. Especially within the range of lower salinity, just a little change of salinity had a dramatic influence on ammonium adsorption by sediments.     

Adsorption of phosphate on tidal flat surface sediments from the Yangtze Estuary

Adsorption of phosphate (PO₄-P) by sediments of nine sites taken from the Yangtze Estuarine and coastal tidal flats were studied in a laboratory. The results indicate that the process of phosphorus adsorption onto sediments mainly occurred within 0-10 h, and then reached a dynamic equilibrium. This experimental finding has shown maximum adsorption rates (ad-R) occurred within 0-0.5 h, ranging from 10.40-56.40 mg/kg h with regional differences. The adsorption rates were obviously related to concentrations of fine particles (<63 µm) in the sediments. Adsorption isotherm curves were fitted to the modified Langmuir equation. Adsorption capacities (ad-C) varied from 26.32 to 204.08 mg/kg, and showed good affinities for Fe³⁺ and TOC concentrations. The adsorption efficiency (ad-E) of phosphate on sediments ranged from 21.55 to 248.30 L/kg, showing a close correlation with TOC concentrations. A correlation between environmental factors and phosphate adsorption is presented in this experiment. Phosphate adsorption is susceptible to changes in pH, temperature and salinity conditions.     

Distribution,chemical speciation and source of trace elements in surface sediments of the Changjiang Estuary

To evaluate biogeochemical characteristics, eco-environmental risks and sources of trace elements (TEs: As, Hg, Se, Sb, Te, Sn, Bi and Ge), their total concentrations and chemical speciation in surface sediments collected from the Changjiang Estuary were determined. Total concentrations for As, Hg, Se, Sb, Te, Sn, Bi and Ge were 4.57–30.20, 0.01–0.40, 0.04–0.38, 0.36–1.48, 0.02–0.10, 0.48–6.58, 0.13–0.64 and 0.83–2.43 μg/g, respectively, with higher values at the estuary. This distribution pattern was attributed to the riverine input and high clay and total organic carbon contents. The sequential extraction suggested that TEs mainly occurred in residual fractions. The risk assessment code suggested that As, Hg and Sn were at low risk, whereas Bi, Se, Sb, Te and Ge were at medium risk. The geoaccumulation index (I _geo) and principal component analysis indicated that Se and Sn mainly came from the natural input (crustal and biological inputs), whereas As, Sb, Hg, Bi and Te came from both of the crustal and anthropogenic inputs via atmosphere and rivers. In addition, Ge possibly came from the natural (crustal and biological inputs) and anthropogenic inputs.     

Modeling solute transport and sulfate reduction in marsh sediments

The seasonal oscillation in sulfate and chloride concentration profiles in some salt marsh sediments is due to exchange of solutes with water on the surface of the marsh, and to the desiccation of the sediment in summer. Desiccation is manifested by disappearance of surface waters, fluctuations in the location of the water table, and by removal of water from the sediment above the water table. The loss of water from the pore space is commonly accompanied by entry of air into the soil, which oxidizes sulfide. The oxidation causes titratable alkalinity to decrease and results in CO₂ degassing.Diffusion models of salinity can account for the observed profiles but only as long as the marsh is maintained inundated. The complexities introduced to the solute transport equations by sediment desiccation invalidate steady-state modeling of solute transport and diagenesis. The concentration profiles of dissolved products of sulfate reduction, such as bicarbonate, require months to reestablish a steady state after being disrupted. If the profiles of dissolved products of sulfate reduction are disrupted seasonally, such as by a seasonal fluctuation in the water table, they may remain transient throughout the year.     

Distribution and reactivity of oxyanions (Sb, As, V, Mo) in the surface freshwater reaches of the Gironde Estuary (France)

The present work reports on the temporal variations of Sb, As, V and Mo concentrations in the surface freshwater reaches of the Gironde Estuary (SW France). Dissolved (<0.2 and <0.02 μm) and particulate Sb, As, V and Mo concentrations were measured in samples collected with high temporal resolution (every 30 min) during two consecutive tides at a fixed station located upstream of the city of Bordeaux and the maximum turbidity zone (MTZ). In addition, measurements of suspended particulate matter concentration, physico-chemical parameters, Cl⁻ concentration, water depth, current velocity and particulate Th concentration were performed either at the same time resolution or continuously. The data obtained suggested that variations in particulate As, V and Mo concentrations were most probably related to tidal cycling near the sampling site of fine grained particles from the MTZ located downstream. Significant differences in the behavior of the dissolved target oxyanions, mostly present in the <0.02 μm fraction, occurred. The behavior of Sb was conservative. Variations of the dissolved As and V concentrations showed similar cycling trends, strongly related to tidal cycles. These As and V cycles were interpreted as a mixing between upstream freshwater and downstream water enriched in dissolved As and V by desorption from the MTZ particles. The observed trend in the variation of the dissolved Mo was more complex than that of As and Sb and attributed to the mixing of the water bodies mentioned above coupled to a point source input of dissolved Mo from an intra-estuarine source. The contribution of this suspected Mo source to the dissolved Mo concentrations measured at the sampling site was estimated from the ratio of dissolved Mo to dissolved As concentrations. The additional dissolved Mo signal, coupled to the monitored ebb and flood length and associated current velocities, suggested an anthropogenic input which may derive from industrial activity near the city of Bordeaux. Extrapolating these results to the annual scale suggested that this dissolved Mo may be equivalent to 45-90% of the annual dissolved Mo flux into the Garonne Branch, highlighting the importance to further investigate the origin and behavior of Mo in the fluvial estuary near Bordeaux.     

长江口吴淞-浏河滨岸带沉积物AVS和SEM含量的空间分布特征

对长江口吴淞-浏河滨岸带37个站位沉积物中酸可挥发性硫化物（AVS）和同时可提取态重金属（SEM）含量及其空间分布特征进行了研究。结果表明,SEM在37个站位沉积物中浓度范围为0．20～1．37μmol／g,平均值为0．74μmol／g;AVS的浓度范围为0．20—0．80μmol／g,平均值为0．23μmol／g;沉积物中AVS含量与总有机碳（TOC）和含水率呈显著正相关关系,而SEM分别与TOC和含水率呈显著正相关关系,与沉积物中值粒径呈显著负相关关系。依据SEM／AVS比值评价方法以及美国EPA（SEM—AVS）差值评价方法对沉积物中重金属的生物有效性的判断表明,除了B2站点无显著生物毒性外,吴淞-浏河滨岸带沉积物中重金属对水生生物均处于中等毒性水平。