Hydrological and biogeochemical dynamics of the minor and trace elements in the St. Lawrence River

Surface water samples from the St. Lawrence River were collected in order to study the processes controlling minor and trace elements concentrations (Al, Fe, Mn, Cd, Co, Cu, Ni and Zn), and to construct mass balances allowing estimates of the relative importance of their natural and anthropogenic sources. The two major water inputs, the upper St. Lawrence River, which drains waters originating from the Lake Ontario, and the Ottawa River were collected fortnightly over 18 months. In addition, other tributaries were sampled during the spring floods. The output was monitored near Quebec City at the river mouth weekly between 1995 and 1999. Dissolved metal concentrations in the upper St. Lawrence River carbonated waters were lower than in the acidic waters of the tributaries draining the crystalline rocks of the Canadian shield and the forest cover. Biogeochemical and hydrodynamic processes occurring in Lake Ontario drive the seasonal variations observed in the upper St. Lawrence River. Biogeochemical processes relate to biological uptake, regeneration of organic matter (for Cd and Zn) and oxyhydroxide formation (for Mn and Fe), while hydrodynamic processes mainly concern the seasonal change in vertical stratification (for Cd, Mn, and Zn). In the Ottawa River, the main tributary, oxyhydroxide formation in summer governs seasonal patterns of Al, Fe, Mn, Cd, Co and Zn. The downstream section of the St. Lawrence River is a transit zone in which seasonal variations are mainly driven by the mixing of the different water masses and the large input of suspended particulate matter from erosion. The budget of all dissolved elements, except Fe and Zn, was balanced, as the budget of particulate elements (except Cd and Zn). The main sources of metals to the St. Lawrence River are erosion and inputs from tributaries and Lake Ontario. Direct anthropogenic discharges into the river accounted for less than 5% of the load, except for Cd (10%) and Zn (21%). The fluxes in transfer of dissolved Cd, Co, Cu and Zn species from the river to the lower St. Lawrence estuary were equal to corresponding fluxes calculated for Quebec City since the distributions of dissolved concentrations of these metals versus salinity were conservative. For Fe, the curvature of the dilution line obtained suggests that dissolved species were removed during early mixing.     

Migration of dissolved trace elements in the mixing zone between Volga River water and Caspian seawater: Results of observations over many years

Based on natural observations over many years, the distribution of dissolved nutrients and trace elements was analyzed in the mixing zone between the freshwater of the Volga River and Caspian seawater. Most of the trace elements (Li, Rb, Cs, B, F, Br, I, Ga, Sc, Y, Co, Ni, Cu, Cd, Ag, V, As, Sb, Bi, Mo, W, and U) show a conservative behavior. During the period of the highest bioproductivity, dissolved phosphates and silica are intensely removed from solution (up to 60–90 and 46–82% of their supply by river runoff, respectively) mostly owing to uptake by aquatic organisms. The distribution of dissolved strontium was assigned to the weakly nonconservative type, because a minor excess of its content above the lines of conservative mixing (8–18%) was observed in some years; perhaps, this is related to different water transformation at the areas of moving and stagnant water in the delta and offshore mouth zone. Barium is characterized by additional input into the solution (up to 52%) in the regions of medium salinity owing to ion exchange reactions in the absorbed complex of river suspended material. The migration of dissolved species of aluminum, manganese, and iron in the mixing zone of Volga and Caspian waters is probably controlled by the coagulation and flocculation of organic and organo-mineral colloids, which is indicated by a sharp decrease in the content of these elements during the initial stage of salinization (59, 91, and 74%, respectively) followed by a plateau. The most complicated distribution was observed for titanium, lead, and rare earth elements (REE), the concentrations of which showed intense removal from the solution (up to 64–88% Ti, 52–87% Pb, and 66–83% REE) followed by a gradual increase, which is probably related to the elevated contents of these elements in the water of the northern Caspian above a local minimum in the zone of active flocculation of colloids.     

Geochemistry of Rare Earth Elements in the Ocean

This work briefly outlines modern ideas on geochemistry of rare earth elements (REE) in the ocean. Sources of REE and chemical properties of these elements, which govern their migration ability in natural processes, are considered. The REE behavior in the river water–seawater mixing zone is analyzed. The fractionation of dissolved and suspended REE in oceanic water in both aerobic and anaerobic conditions is also considered. It is shown that the variability of REE composition in pelagic sediments reflects the fractionation of these elements in the oceanic water as a consequence of material differentiation in the ocean. The REE distribution in terrigenous, authigenic, hydrothermal, and biogenic constituents of sediments, such as clay, bone debris, barite, phillipsite, Fe–Mn oxyhydroxides (ferromanganese nodules and micronodules), Fe–Ca hydroxo-phosphate, diatoms, and foraminifers, is considered.     

The transport of Osmium and Strontium isotopes through a tropical estuary

We have determined the concentration and isotopic composition of Os and Sr in the estuarine waters from the Godavari delta in Peninsular India. Additionally, we have obtained the concentration and isotopic composition of Os and Al concentration in selected suspended particulate matter recovered on 0.45 μm filters. The Na, K, Mg, and Ca concentrations of water samples obtained along salinity gradients from two distributary channels in the delta display a general two component mixing between river- and sea-water. The data also reveal that Al behaves non-conservatively and is affected by interactions with suspended particulates. The ⁸⁷Sr/⁸⁶Sr ratio of the riverine end member is 0.716303 and shows a linear decrease with salinity to seawater value and Sr isotope systematics indicate that its behavior is conservative in the estuary.The ¹⁸⁷Os/¹⁸⁸Os ratio of the Godavari river end-member is 1.24 and within error of the average eroding upper continental crust. The concentration and isotopic composition of Os through the two salinity transects shows that its behavior in the Godavari estuary is complex and non-conservative. By comparing the Al/Os ratios and Os isotopes in the waters with those of the suspended particulate we find that both Os gains and losses occur in the water column. However, in one of the distributaries (Vasishta) the Os concentration of suspended load increases and that of dissolved load decreases with increasing salinity towards the Bay of Bengal end-member. We infer that there is removal of seawater Os at higher salinities. The estimated mean residence time of Os in the oceans is 37 ± 14 (2σ) kyr. A comparison of the Os concentration of the Bay of Bengal and the Indian Ocean waters indicates that the rainout rate of Os in Bay of Bengal is 30% faster than that in the open ocean and suggests that the observed discrepancy between the mean residence time calculated from mass balance considerations and that estimated from the relaxation of the Os isotopic ratio in marine record may not be real as the relaxation time experiments likely estimate the residence time for a basin/sub-basin and not for the entire ocean.     

Behaviour of rare earth elements at the freshwater–seawater interface of two acid mine rivers: the Tinto and Odiel (Andalucia, Spain)

The concentrations of dissolved and suspended particulate rare-earth elements (REE) are reported in acid-sulphate waters from the Odiel and Tinto rivers. Shale normalized patterns are typically convex and high REE concentrations (e.g., Ce=0.43–65 μg.l⁻¹) are present in the waters. The REE content of the suspended load is greater by a factor of up to 3000. In the Odiel river, REE patterns of the particulates are essentially convex and sub-parallel to those of the waters; speciation calculations indicate that SO₄ complexes play a dominant role in controlling the REE distributions. In the Tinto river, the REE patterns of the suspended load are slightly fractionated and a negative Ce anomaly is apparent in several samples, reflecting the local influence of phosphogypsum deposits.Contrasting with normal estuaries, REE are not intensely removed in the low chlorinity zone. A remobilization in relation to Fe reduction is observed in the Tinto river.     

Behavior of Uranium in the Yellow River Plume (Yellow River Estuary)

The Yellow River (Huanghe) is the second largest river in China and is known for its high turbidity. It also has remarkably high levels of dissolved uranium (U) concentrations (up to 38 nmol 1^-1). To examine the mixing behavior of dissolved U between river water and seawater, surface water samples were collected along a salinity gradient from the Yellow River plume during September 2004 and were measured for dissolved U concentration,²³⁴U:²³⁸U activity ratio, phosphate (PO₄ ^3–), and suspended particulate matter. Laboratory experiments were also conducted to simulate the mixing process in the Yellow River plume using unfiltered Yellow River water and filtered seawater. The results showed a nonconservative behavior for dissolved U at salinities < 20 with an addition of U to the plume waters estimated at about 1.4 X 10⁵ mol yr^–1. A similarity between variations in dissolved U and PO₄ ^3– with salinity was also found. There are two major mechanisms, desorption from suspended sediments and diffusion from interstitial waters of bottom sediments, that may cause the elevated concentrations of dissolved U and PO₄ ^3– in mid-salinity waters. Mixing experiments indicate that desorption seems more responsible for the elevated dissolved U concentrations, whereas diffusion influences more the enrichment of PO₄ ^3–.     

Aquatic hydrocarbon distributions in the Seine estuary: Biogenic polyaromatics and n-alkanes

Dissolved and particulate hydrocarbons of biogenic origin were investigated for the first time in surface waters along the Seine River and its estuary. They comprise n-alkanes (n-ALKs) and diagenetic polycyclic aromatic hydrocarbons (PAHs). Samples were collected in three different sections of the estuary: the riverine zone, the mixing zone, and the marine zone. At the river mouth, two mooring stations were used for the collection of samples over tidal cycles. Total particulate n-ALK concentrations ranged from 31 ng 1^?1 to 2,918 ng 1^?1, or 5 μg g^?1 dry ng 1^?1, or 2 μg g^?1 of SM. Concentrations varied with the SM load and could be related to sedimentation and estuarine mixing. The sources of the n-ALKs were different in each zone of the estuary. The dissolved n-ALKs displayed lower concentrations than the particulate phase, varying from 136 ng 1^?1 to 344 ng 1^?1, while biogenic dissolved PAHs were almost absent.     

Global Nitrogen Cycle: Pre-Anthropocene Mass and Isotope Fluxes and the Effects of Human Perturbations

We present a nitrogen cycle model for pre-industrial times based on an extensive literature database. The model consists of 18 reservoirs in the domains of the atmosphere, land, and ocean. The biotic reservoirs on land and in the ocean (N-fixing plants, non-N-fixing plants, and marine biota) interact with atmospheric N₂ and dissolved inorganic nitrogen (DIN, consisting of N₂, NO₃ ^?, and NH₄ ⁺) in the ocean and soil waters. Marine DIN is taken up by marine biota and transformed from ocean particulate organic matter to dissolved organic nitrogen and the ocean sediment. The atmosphere, the largest nitrogen reservoir, supplies N₂ to the system by N fixation, deposition, and dissolution, and these input fluxes are balanced by denitrification and volatilization back to the atmosphere. The land and ocean domains are linked by river transport, which carries both dissolved and particulate nitrogen to the oceanic coastal zone. The isotope–mass balances of the N reservoirs are calculated from the isotopic composition of the reservoirs and the fractionation factors accompanying the fluxes between the reservoirs based on reported values from different natural conditions. The model sensitivity was tested for different biouptake rates and was run with various human perturbations, including fertilization, nitrous oxide emissions, population-related sewage disposal, land-use changes, and temperature-dependent rate kinetics. The new N mass–isotope cycle model provides the basis for assessment of the impact of artificial fertilization between 1700 and 2050. The perturbation experiments in this study suggest that land-use change is the key factor altering the N mass cycle since industrialization.     

Comparison of controlling mechanisms of flocculation processes in estuaries

During estuarine mixing, dissolved metals come into the particulate phase due to the flocculation processes. Such processes are biologically vital. In the present study, controlling mechanisms of elemental flocculation during estuarine mixing in northern and southern estuaries of Iran in relation to the various physical and chemical parameters of waters have been compared. Except for zinc and lead, for other studied elements in Minab River, water flocculate at higher rates in comparison with the rivers flowing into the Caspian Sea. Redox potential might have negative effect on flocculation process in Minab Estuary. Contrary to rivers flowing into the Caspian Sea, in Minab River elemental flocculation is governed by dissolved organic carbon and it shows a non-liner and conservative behavior during estuarine mixing which implies that dissolved organic carbon originates from terrigenous source. The results also shows that maximum removal of elements occurs in lower salinities (1.5 to 5.8 ‰) for the rivers in North of Iran and 3.3 to 11.4 ‰ for Minab River in South of Iran. Flocculation of studied metal in different rivers results in reduction of overall metal pollution load by various percentages. The initial metal contents on river water and mean discharge of river might lead to higher flocculation rates.     

Variability of Stable Isotope Fingerprints of the Serpulid Ficopomatus enigmaticus Within a Permanently Stratified Estuary: Implications for (Palaeo)environmental Interpretations

This paper examines how the mixing of freshwater and seawater, and related mixing of freshwater and marine particulate organic matter (POM) in the permanently stratified estuary of the River Krka, Croatia, are reflected in the stable isotope fingerprints of soft tissues and tubes of the serpulid Ficopomatus enigmaticus. The carbon stable isotope composition (δ¹³C values) of the river-borne POM is retained over long distances, causing a depletion in ¹³C of POM in brackish waters. A trophic depletion in ¹³C was recorded in serpulid soft tissues. The serpulid carbonate tubes were depleted in ¹³C even at locations with salinity close to that of the sea and were subject to large isotope fractionation between dissolved inorganic C (DIC) and carbonate caused by vital effects, making carbonate depleted in ¹³C by several per mil compared with DIC. These effects, though large in the freshwater zone, fade towards the sea. The carbonate δ¹⁸O values of tubes reflect the δ¹⁸O values of the water. The temperature-related differences in δ¹⁸O values of tubes from different sites are masked by source-related differences in the δ¹⁸O values of water arising from mixing of freshwater and seawater in the estuary. Therefore, in serpulide tubes, the terrestrial component can easily be overestimated because of vital effects during biomineralisation and trophic depletion in ¹³C in freshwater and brackish environments.     

Mixing Deposition of Upper Carboniferous in Jiangshan, Zhejiang Province and its Tectonic Significance

<正>The Outangdi Formation in Jiangshan,Zhejiang,is the mixing deposit of terrigenous clastics and carbonates in Weiningian of the late Carboniferous.The mixing deposits include interbeddings, which constitute a series of alternated clastic and carbonate beds and mixing within the same bed which forms"hunji rock".The Outangdi Formation has the features of intercalated marine and terrestrial deposits with the progradational sequences,which are lower fine and upper coarse sedimentary granularity in the section.Hunji rock is formed in a seashore environment.It is a mixed carbonate sediment found in beaches or tideland facies with quartz sand taken from a bayou or beach by coastwise flow and circumfluence.There are two kinds of hunji sequences:(1) interbeds of sandstone and carbonate rock in seashore environments;and(2) interbeds of clastics in river facies and carbonate rock in ocean facies.It is indicated that mixing depositions belong to"facies mixing",affected mainly by regional tectonic uplift,rise of the global sea level,and the dynamics of water medium in the basin. Regional sea level periodic changes and progradational sequences probably resulted from the intense uplift of the old land called Cathaysia.The classification and name of mixed sediments are also discussed in the present study.Interbeds and alternated beds of clastic and carbonate beds are named"hunji sequence",a new genetic term.It is suggested that hunji rock means a special sediment event of mixing terrigenous clastics and carbonates instead of a name of a specific rock.     

Trace element cycling in a subterranean estuary: Part 2. Geochemistry of the pore water

Submarine groundwater discharge (SGD) is an important source of dissolved elements to the ocean, yet little is known regarding the chemical reactions that control their flux from sandy coastal aquifers. The net flux of elements from SGD to the coastal ocean is dependent on biogeochemical reactions in the groundwater-seawater mixing zone, recently termed the “subterranean estuary.” This paper is the second in a two part series on the biogeochemistry of the Waquoit Bay coastal aquifer/subterranean estuary. The first paper addressed the biogeochemistry of Fe, Mn, P, Ba, U, and Th from the perspective of the sediment composition of cores Charette et al. [Charette, M.A., Sholkovitz, E.R., Hansell, C.M., 2005. Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments. Geochim. Cosmochim. Acta, 69, 2095-2109]. This paper uses pore water data from the subterranean estuary, along with Bay surface water data, to establish a more detailed view into the estuarine chemistry and the chemical diagenesis of Fe, Mn, U, Ba and Sr in coastal aquifers. Nine high-resolution pore water (groundwater) profiles were collected from the head of the Bay during July 2002. There were non-conservative additions of both Ba and Sr in the salinity transition zone of the subterranean estuary. However, the extent of Sr release was significantly less than that of its alkaline earth neighbor Ba. Pore water Ba concentrations approached 3000 nM compared with 25-50 nM in the surface waters of the Bay; the pore water Sr-salinity distribution suggests a 26% elevation in the amount of Sr added to the subterranean estuary. The release of dissolved Ba to the mixing zone of surface estuaries is frequently attributed to an ion-exchange process whereby seawater cations react with Ba from river suspended clay mineral particles at low to intermediate salinity. Results presented here suggest that reductive dissolution of Mn oxides, in conjunction with changes in salinity, may also be an important process in maintaining high concentrations of Ba in the pore water of subterranean estuaries. In contrast, pore water U was significantly depleted in the subterranean estuary, a result of SGD-driven circulation of seawater through reducing permeable sediments. This finding is supported by surface water concentrations of U in the Bay, which were significantly depleted in U compared with adjacent coastal waters. Using a global estimate of SGD, we calculate U removal in subterranean estuaries at 20 × 10⁶ mol U y⁻¹, which is the same order of magnitude as the other major U sinks for the ocean. Our results suggest a need to revisit and reevaluate the oceanic budgets for elements that are likely influenced by SGD-associated processes.     

Hydrodynamics of suspended particulate matter in the tidal freshwater zone of a macrotidal estuary (the Seine Estuary, France)

The effects of fortnightly, semidiurnal, and quaterdiurnal lunar tidal cycles on suspended particle concentrations in the tidal freshwater zone of the Seine macrotidal estuary were studied during periods of medium to low freshwater flow. Long-term records of turbidity show semidiurnal and spring-neap erosion-sedimentation cycles. During spring tide, the rise in low tide levels in the upper estuary leads to storage of water in the upper estuary. This increases residence time of water and suspended particulate matter (SPM). During spring tide periods, significant tidal pumping, measured by flux calculations, prevents SPM transit to the middle estuary which is characterized by the turbidity maximum zone. On a long-term basis, this tidal pumping allows marine particles to move upstream for several tens of kilometers into the upper estuary. At the end of the spring tide period, when the concentrations of suspended particulate matter are at their peak values and the low-tide level drops, the transport of suspended particulate matter to the middle estuary reaches its highest point. This period of maximum turbidity is of short duration because a significant amount of the SPM settles during neap tide. The particles, which settle under these conditions, are trapped in the upper estuary and cannot be moved to the zone of maximum turbidity until the next spring tide. From the upper estuary to the zone of maximum turbidity, particulate transport is generated by pulses at the start of the spring-neap tide transition period.     

Distribution and composition of suspended particulate matter in the Atlantic Ocean: Direct measurements and satellite data

The main purpose of this work is to study the real distribution and spatial–temporal variations of suspended particulate matter and its main components in surface waters of the Atlantic Ocean on the basis of direct and satellite measurements for development of new and perfection of available algorithms for converting satellite data. The distribution fields of suspended particulate matter were calculated and plotted for the entire Atlantic Ocean. It is established that its distribution in the open ocean is subordinate to the latitudinal climatic zonality. The areas with maximum concentrations form latitudinal belts corresponding to high-productivity eutrophic and mesotrophic waters of the northern and southern temperate humid belts and with the equatorial humid zone. Phytoplankton, the productivity of which depends primarily on the climatic zonality, is the main producer of suspended particulate matter in the surface water layer.     

The concept of a equilibrium surface applied to particle sources and contaminant distributions in estuarine sediments

Studies have shown that many chemically-reactive contaminants become associated with fine particles in coastal waters and that the rate, patterns, and extent of contaminant accumulation within estuarine systems are extremely variable. In this paper, we briefly review our findings concerning the accumulation patterns of contaminants in several estuarine systems along the eastern coastline of the United States, and have applied a well-established concept in geology, that is “an equilibrium profile,” to explain the observed large variations in these patterns. We show that fine-particle deposition is the most important factor affecting contaminant accumulation in estuarine areas, and that accumulation patterns are governed by physical processes acting to establish or maintain a sediment surface in dynamic equilibrium with respect to sea level, river discharge, tidal currents, and wave activity. Net long-term particle and particle-associated contaminant accumulations are negliglible in areas where the sediment surface has attained “dynamic equilibrium” with the hydraulic regime. Contaminant, accumulation in these areas primarily occurs by the exchange of contaminant-poor sedimentary particles with contaminant-rich suspended particles during physical or biological mixing of the surface sediment. Virtually the entire estuarine particulate and contaminant load bypasses these “equilibrium” areas to accumulate at extremely rapid in relatively small areas that are temporally out of equilibriums as a result of natural processes or human activities. These relatively small areas serve as major sinks for particles from riverine and marine sources, and for biogenic carbon formed in situ within estuaries or on the inner shelf.     

Tidal Freshwater Wetlands: Variation and Changes

Tidal freshwater wetlands (TFW) are situated in the upper estuary in a zone bordered upstream by the nontidal river and downstream by the oligohaline region. Here, discharge of freshwater from the river and the daily tidal pulse from the sea combine to create conditions where TFW develop. TFW are often located where human population density is high, which has led to wetland degradation or destruction. Globally, TFW are largely restricted to the temperate zone where the magnitude of annual river discharge prevents saline waters from penetrating too far inland. The constant input of river water delivers high loads of sediments, dissolved nutrients, and other suspended matter leading to high sedimentation rates and high nutrient levels. Prominent biogeochemical processes include the transformation of nitrogen by bacteria and immobilization of phosphate. A diverse, characteristic vegetation community develops which supports a rich fauna. Biotic diversity is highest in the high marsh areas and decreases in the lower levels where tidal inundation is greatest. Benthic fauna is rather poor in diversity but high in biomass compared to other regions of the estuary. Global climate change is a threat for this system directly by sea level rise, which will cause brackish water to intrude into the fresh system, and indirectly during droughts, which reduce river discharge. Salinity will affect the presence of flora and fauna and facilitates sulfate reduction of organic matter in the soil. Increased decomposition of organic matter following saltwater intrusion can result in a lowering of wetland surface elevation. The papers assembled in this issue focus on how these tidal freshwater wetlands have changed over recent time and how they may respond to new impacts in the future.     

The contrasting biogeochemistry of iron and manganese in the Pacific Ocean

Vertical and horizontal distributions of dissolved and suspended particulate Fe and Mn, and vertical fluxes of these metals (obtained with sediment traps) were determined throughout the Pacific Ocean. In general, dissolved Fe is low in surface and deep waters (0.1 to 0.7 nmol/kg), with maxima associated with the intermediate depth oxygen minimum zone (2.0 to 6.6 nmol/kg). Vertical distributions of dissolved Mn are similar to previous reports, exhibiting a surface maximum, a subsurface minimum, a Mn maximum layer coincident with the oxygen minimum zone, and lowest values in deep waters.Near-shore removal processes are more intense for dissolved Fe than for dissolved Mn. Dissolved Mn in the surface mixed layer remains elevated much farther offshore than dissolved Fe. Elevated near-surface dissolved Mn concentrations occur in the North Pacific Equatorial Current, suggesting transport from the eastern boundary. Near-surface mixed-layer dissolved Mn concentrations are higher in the North Pacific gyre reflecting enhanced northern hemisphere aeolian sources.Residence time estimates for the settling of refractory paniculate Fe and Mn from the upper water column are 62–220 days (Fe), and 105–235 days (Mn). In contrast, residence times for the scavenging of dissolved Fe and Mn are 2–13 years (Fe) and 3–74 years (Mn). Scavenging residence times for dissolved Mn based on horizontal mixing in the surface mixed layer of the northeast Pacific are 0.4 years (nearshore) to 19 years (1000 km offshore).There is no evidence for in situ Fe redox dissolution within sub-oxic waters in the eastern tropical North Pacific. Dissolved Fe appeared to be controlled by dissolution from sub-oxic sediments, with oxidative scavenging in the water column or upper sediment layers. However, in situ Mn dissolution within the oxygen minimum zone was evident.     

The effects of the San Francisco Bay plume on trace metal and nutrient distributions in the Gulf of the Farallones

The distributions of particulate elements (Al, P, Mn, Fe, Co, Cu, Zn, Cd, and Pb), dissolved trace metals (Mn, Fe, Co, Cu, Zn, and Cd), and dissolved nutrients (nitrate, phosphate, and silicic acid) were investigated in the Gulf of the Farallones, a region of high productivity that is driven by the dynamic mixing of the San Francisco Bay plume, upwelled waters, and California coastal surface waters. Particulate metals were separated into >10 and 0.4-10 μm size-fractions and further fractionated into leachable (operationally defined with a 25% acetic acid leach) and refractory particulate concentrations. Dissolved metals (< 0.4 μm pore-size filtrate) were separated into colloidal (0.03-0.4 μm) and soluble (<0.03 μm) fractions. The percent leachable particulate fractions ranged from 2% to 99% of the total particulate concentration for these metals with Mn and Cd being predominantly leachable and Fe and Al being predominantly refractory. The leachable particulate Pb concentration was associated primarily with suspended sediments from San Francisco Bay and was a tracer of the plume in coastal waters. The particulate trace metal data suggest that the leachable fraction was an available source of trace metal micronutrients to the primary productivity in coastal waters. The dissolved trace metals in the San Francisco Bay plume and freshly upwelled surface waters were similar in concentration, with the exception of Cu and Co, which exhibited relatively high concentrations in plume waters and served as tracers of this water mass. The dissolved data and estimates of the plume dynamics suggest that the impact of anthropogenic inputs of nutrients and trace metals in the San Francisco Bay plume contributes substantially to the concentrations found in the Gulf of the Farallones (10-50% of estimated upwelled flux values), but does not greatly disrupt the natural stoichiometric balance of trace metal and nutrient elements within coastal waters given the similarity in concentrations to sources in upwelled water. In all, the data from this study demonstrate that the flux of dissolved nutrients and bioactive trace metals from the San Francisco Bay plume contribute to the high and relatively constant phytoplankton biomass observed in the Gulf of the Farallones.     

Desorption and coagulation of trace elements during estuarine mixing

Mixing experiments of seawater and the Hudson and Mississippi riverwaters with radiotracer spikes show that Co, Mn, Cs, Cd, Zn and Ba will be desorbed from river suspended particles, while significant fractions of “dissolved” Fe, Sn, Bi, Ce and Hg will be coagulated during estuarine mixing.     

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.