Mercury distribution in Douro estuary (Portugal)

Determinations of dissolved reactive and total dissolved mercury, particulate and sedimentary mercury, dissolved organic carbon (DOC), particulate organic carbon (POC) and suspended particulate matter (SPM) have been made in the estuary of river Douro, in northern Portugal. The estuary was stratified by salinity along most of its length, it had low concentrations of SPM, typically <20 mg dm(-3), and concentrations of DOC in the range <1.0-1.8 mg dm(-3). The surface waters had a maximum dissolved concentration of reactive mercury of about 10 ng dm(-3), whereas for the more saline bottom waters it was about 65 ng dm(-3). The surface waters had maximum concentrations of total suspended particulate mercury of approximately 7 microg g(-1) and the bottom waters were always <1 microg g(-1). Concentrations of mercury in sediments was low and in the range from 0.06 to 0.18 microg g(-1). The transport of mercury in surface waters was mainly associated with organic-rich particulate matter, while in bottom waters the dissolved phase transport of mercury is more important. Lower particulate organic matter, formation of chlorocomplexes in more saline waters and eventually the presence of colloids appear to explain the difference of mercury partitioning in Douro estuarine waters.     

Dissolved and particulate fluxes of copper through the Morlaix river estuary (Brittany, France): mass balance in a small estuary with strong agricultural catchment

Dissolved and particulate copper were measured over an annual cycle (12 surveys between February 1998 and January 1999) in the Morlaix Estuary (Brittany, France). These variations were investigated in both the water column and the benthic compartment in order to calculate fluxes of copper within estuary. In the water column, dissolved and particulate copper concentrations ranged from 0.6 to 19.0 nM and from 0.03 to 2.3 micromol g(-1), respectively. In the benthic compartment, copper concentrations in superficial sediment varied from 0.04 to 0.32 micromol g(-1) and from 7.6 to 80.5 nM in the pore waters. The results show that copper contents in the water column reached levels commonly observed in estuaries affected by heavy industrial activities. Agricultural activities, extensively developed on the drainage basin, may be responsible for the copper excess. Mass balance of copper indicates that the metal accumulated within the estuary with a rate ranging from 97 to 119 kg yr(-1).     

Dissolved and particulate trace metal fluxes through the central English Channel, and the influence of coastal gyres

Measurements of dissolved Cd, Co, Cu, Mn, Ni, Pb, and Zn have been made on a seasonal basis at five stations on a north–south transect across the central English Channel between Cherbourg and the Isle of Wight. Vertical and horizontal distributions of dissolved Cd, Pb, Cu and Zn are relatively uniform except for sampling sites near the English coast. Dissolved Mn and Co show increased concentrations in the English coastal waters, and for Mn the seasonal trend in concentration follows the pattern seen in the Strait of Dover with higher values in the late summer. Ni and Cu are higher in concentration on the English side, which reflects mainly riverine sources. Measurements were also made of particulate forms of the metals above plus particulate Al, Ca, Fe, Mg, Sr and Ti. Water column concentrations of particulate metals broadly follow the distribution of suspended particulate matter, with highest concentrations near the UK coast. Trace metal concentrations have been integrated with modelled data on fluxes of water to provide estimates of fluxes for these elements into the eastern Channel, and an initial comparison is made with data for fluxes of metals through the Strait of Dover obtained during an earlier study. A major influence on the fluxes of particulate metals through the Isle of Wight-Cherbourg transect is the gyre system to the South east to the Isle of Wight, which has important east to west as well as west to east transport components. For those elements where the dissolved form of the metal dominates, the large flow of water in the central Channel waters leads to major fluxes of the metals towards the east and the Strait of Dover. However, the high suspended particulate matter loadings in the coastal waters and impact of the gyre system lead to net east to west fluxes of particulate Al, Fe, Mn and Ti. Comparison of these fluxes with data on the net west to east transport of these materials through the Strait of Dover infers that there must be a significant supply of these particulate metals to the eastern Channel.     

Lead and copper in the waters of Raritan and Lower New York Bays

A survey of waters adjacent to this heavily urbanized and industrialized region showed concentrations of copper, 65 μg l.^?1 to be the highest reported to date for estuarine waters, and lead up to 13.9 μg l.^?1 Correlations between distributions of dissolved and total metal concentration in the water column, hydrography, and metal in the sediment were related to benthic studies in this area. Laboratory studies are cited which show the potential for adverse effects on marine animals at these metal concentrations.     

Distribution and fluxes of metals in the St. Lawrence River from the outflow of Lake Ontario to Québec City

Six anchor stations in the St. Lawrence River from the outflow of Lake Ontario to Quebec City, were occupied for ca. 24 hours in June 1987 during low flow conditions. Samples of water and suspended particulate matter were separated by continuous-flow centrifugation, and were collected every two hours.During this sampling period, fluxes of dissolved forms of zinc, copper and nickel increased in Lac St. François and downstream relative to the sum of the fluxes for the two upstream stations at the outflow of Lake Ontario. Increases in the flux of dissolved zinc and copper were pronounced below Montreal and above Lac St. Pierre. For particulate forms of metals, all five metals show that there are significant inputs in the section of the St. Lawrence River between Lac St. François and the station just above the entrance to Lac St. Pierre.The average concentrations of dissolved cadmium, lead, zinc, copper and nickel ranged from 7–23 ng/l; 9–35 ng/l; 0.434–0.939 g/l; 0.15–0.89 g/l and 0.58–1.12 g/l respectively.Regression analysis of the dissolved and particulate metal concentrations suggests that the concentration of dissolved cadmium, lead, zinc and nickel can be predicted from the regression equation and the determination of particulate metal concentration. This prediction appears to be independent of the suspended particulate matter concentration which varies from ca. 1 to 10 mg/l from the outflow of Lake Ontario to Québec City.     

Migration of Lead-210 and Stable Load in Surface Waters Impacted by Uranium Mine Wastes

Water and sediment samples from two surface water systems were analysed for ²¹⁰Pb and stable lead in order to elucidate the environmental importance and fate of ²¹⁰Pb released from uranium mining. In one system mine drainage waters treated by precipitation of barium sulfate contained a considerable activity of ²¹⁰Pb in particulate form. Spoil piles were the main source of ²¹⁰Pb in the second system, with the dissolved ²¹⁰Pb being the predominant migration form. In both systems the concentration of ²¹⁰Pb rapidly decreased with distance from the source indicating that waterborne ²¹⁰Pb did not represent an environmental problem. Uranium mining did not add significant amounts of stable lead into the surface water systems. It has been found that bottom sediments are a sensitive indicator of the pollution of surface waters with ²¹⁰Pb.     

The distribution of dissolved copper in the eastern Atlantic Ocean

Dissolved copper concentrations at five stations in the eastern Atlantic between 20 and 24°N are presented. The metal is depleted in surface waters with concentrations ranging from 1.1 to 1.7 nmol/l. Marked increases in concentration were found in near-bottom waters with levels up to 10.9 nmol/l; these are attributed to the release of dissolved copper from the surface sediment.     

Sublethal effects of contamination on the Mediterranean sponge Crambe crambe: metal accumulation and biological responses

The effect of low levels of pollution on the growth, reproduction output, morphology and survival of adult sponges and settlers of the sponge Crambe crambe were examined. We transplanted sponges from a control area to a contaminated site and measured the main environmental variables (chemical and physical) of both sites during the study period. Except some punctual differences in particulate organic matter, silicates, nitrates, and water motion, most environmental variables in the water were similar at both sites during the study months. Mainly copper, lead and OM concentrations in the sediment, and water motion were significantly higher at the polluted site and may be implicated in the biological effects observed: decrease in the percentage of specimens with embryos, increase in shape irregularity and decrease in growth rate. Individuals naturally occurring at the polluted site and those transplanted there for four months accumulated ten times more copper than either untouched or transplant controls. Although lead concentration in sediment did not differ between sites, native specimens from the contaminated site accumulated this metal more than untouched controls. Vanadium concentration also tended to increase in the sponges living at or transplanted to the contaminated site but this difference was not significant. C. crambe is a reliable indicator of metal contamination since it accumulates copper, lead and vanadium in high amounts. At the contaminated site, sponge growth, fecundity and survival were inhibited, whereas sponge irregularity ending in sponge fission was promoted. All these effects may compromise the structure and dynamics of the sponge populations in sheltered, metal-contaminated habitats.     

Dispersion of dissolved trace metals from the Irish Sea into Scottish coastal waters

An investigation has been undertaken into the dispersal of contaminants from the Irish Sea into coastal waters of Scotland via the North Channel. A total of 97 surface samples have been analysed for dissolved copper, cadmium and lead. Salinity and reactive phosphate have also been determined. Evidence is presented to suggest that copper, cadmium and reactive phosphate behave essentially conservatively on mixing into Scottish coastal waters. This behaviour is likened to the dispersal of¹³⁷Cs from the Sellafield nuclear fuel reprocessing plant. It is suggested that this simple mechanism is inadequate to account for the lead distribution. It is proposed that this element is partly taken up by suspended particulates and sediments in the well-mixed turbid waters of the North Channel.It has been demonstrated elsewhere that contaminants from the Irish Sea, such as¹³⁷Cs enter the Firth of Clyde from the North Channel. In the present study North Channel waters are demonstrated to be an important source of trace metals to the Firth of Clyde. At the time of this survey however high concentrations of trace metals were not entering the Firth of Clyde from the North Channel. This is principally attributed to a salinity front associated with the entrance of the Firth which hinders transport across the sill.     

The use of transplanted cultured tropical oysters (Saccostrea commercialis) to monitor Cd levels in North Queensland coastal waters (Australia)

Bivalves are commonly used to detect metal pollution in the marine environment. Commercially cultured Milky oysters (Saccostrea commercialis) were transplanted in various sites along the North Queensland coast and analyzed for two metals of potentially anthropogenic origin (Cd, Zn). To provide additional information, naturally occurring Black Lip oysters (Saccostrea echinata) were also collected at the transplantation sites. The study demonstrated that the oysters species transplanted are good bioindicators of these metal concentrations in tropical waters, sensitive to variations in the environment at concentrations which are much smaller than pollution signals commonly reported for temperate waters. Three transplant experiments were carried out from May 1999 to February 2000. Milky oysters transplanted to offshore areas (Orpheus Is., Kelso Reef) accumulated Cd in the soft parts whereas oysters sampled from cages placed in Ross Creek and the Herbert River estuaries showed a decrease in Cd concentration, which resulted from an increase in dry weight. Dry weight appeared to be an important covariant affecting Cd concentration in the oysters whereas it does not unambiguously affect Zn concentrations. For the duration of the experiments, oysters sampled from the Magnetic Is. reference site showed effectively constant Cd concentrations and total Cd contents which indicates that any seasonal cycle affecting metal concentration is weak. It was found that Cd accumulation in oysters increased as ambient dissolved Cd concentration decreased, from which it was concluded that for these oysters, the predominant source of Cd was from the particulate phase rather than the dissolved phase.     

Iron in the southeastern Bering Sea: Elevated leachable particulate Fe in shelf bottom waters as an important source for surface waters

Surface transects and vertical profiles of total and leachable particulate Fe, Mn, Al and P, along with dissolved and soluble Fe were obtained during August 2003 in the southeastern Bering Sea. High concentrations of leachable particulate Fe were observed in the bottom waters over the Bering Sea shelf with an unusually high percentage of the suspended particulate Fe being leachable. Leachable particulate Fe averaged 81% of total particulate Fe, and existed at elevated concentrations that averaged 23 times greater than dissolved Fe in the isolated cool pool waters over the mid shelf where substantial influence of sedimentary denitrification was apparent. The elevated leachable particulate Fe is suggested to be a result of sedimentary Fe reduction in surficial sediments, diffusion of Fe(II) from the sediments to the bottom waters, and subsequent oxidation and precipitation of reduced Fe in the overlying bottom waters. Eddies and meanders of the Bering Slope Current can mix this Fe-rich water into the Green Belt at the outer shelf-break front. Elevated levels of leachable particulate Fe were observed in surface waters near the Pribilof Islands where enhanced vertical mixing exists. Storm events and/or cooling during fall/winter with the resultant destruction of the thermally stratified two-layer system can also mix the subsurface water into surface waters where the elevated leachable particulate Fe is a substantial source of biologically available Fe.     

Copper,zinc and cadmium in coastal waters of the N.W. Mediterranean

The concentration levels of copper, zinc and cadmium in the coastal waters of the northwestern Mediterranean tend to match closely those of off-shore waters when there is no significant man-made contamination. The appearance of local high concentration for one metal by possible contamination does not necessarily correlate with high values for other metals, although some contamination sources elevate the concentrations of all three metals. In June 1974, the presence of a water mass having relatively high surface zinc-concentration was observed off the Marseille-Toulon area.     

Copper,zinc, cadmium,nickel, iron and manganese in the Southern Bight of the North Sea

Ni, Cd, Cu, Zn, and Fe were determined in water and suspended matter samples and Mn in suspended matter samples from the Southern Bight region of the North Sea. Four distinct areas, comprising the Rhine estuary, the Dutch coastal waters, the centre of the Bight, and the English coastal water can be distinguished on the basis of the distribution of the trace metals. The total concentrations of all metals were high in the Rhine estuary, decreased in a seaward direction to reach very low values, comparable to continental shelf water, in the centre of the Bight, and increased again towards the English coast. Elevated concentrations of dissolved Cu, Ni, Cd and Zn near the English coast are not only due to river inputs. Over the entire region, the fraction of Cd, Ni and Zn in solution was consistently more important than the fraction in the suspended particulate phase. In contast, the fraction of Fe and Mn in the solid phase was consistently greater than the fraction in solution. Total concentrations of Fe, Mn and Cu are more dictated by the suspended particulate matter concentration than Cd, Ni and Zn.     

Disequilibria betweenRa, Pb and Po in the Arctic Ocean and the implications for chemical modification of the Pacific water inflow

Measurements have been made of²²⁶Ra and both dissolved and particulate forms of²¹⁰Pb and²¹⁰Po in a vertical profile at 85°50′N, 108°50′W in the Arctic Ocean.In the upper water column²²⁶Ra shows a concentration maximum that is coincident with one in the nutrients, silicate, phosphate, and nitrate, while at the same depth, dissolved and particulate²¹⁰Pb and²¹⁰Po all show minimum concentrations. It is suggested that the concentration maxima are partly due to sources of the respective elements in the continental shelf sediments, the shelf waters being subsequently advected into the Arctic Ocean basins. The²¹⁰Pb and²¹⁰Po minima have similarly been explained by interaction between the shelf sediments and overlying waters. An estimate is made of the possible contributions of shelf sediments to the layer of silica-rich water which covers the Canada Basin at a depth of 100–150 m.Residence times have been calculated for dissolved²¹⁰Pb and²¹⁰Po at various depths in the water column. Surface water residence times of dissolved and particulate forms of these radionuclides are longer than in surface Atlantic waters, probably due to lower biological activity in the surface waters of the Canada Basin. An estimatee has been made of the average sinking velocity of particulate material.     

On the significance of wind event frequency for particulate resuspension and light attenuation in coastal waters

Wind-induced resuspension of particulate matter was investigated in a shallow coastal region off southwestern Australia, chosen for its isolation from the complexity of other confounding physical processes. The site had negligible river discharge, low nutrient concentrations and was largely devoid of tidal currents. Moorings were deployed in the micro-tidal waters to measure current speed, wave parameters, backscatter, subsurface irradiance and dissolved oxygen concentration. Two contrasting sites were chosen as representative of high and low wave-energy environments. Turbulent kinetic energy, recorded by the instruments, was dominated by the wind-wave signal. During wind events, at the most exposed site, bed shear stress exceeded the critical stress required to lift and resuspend sediments. At the most enclosed site, bed shear stresses only exceeded the critical stress required to suspend less dense material such as benthic fluff. Wind-waves were found to be the dominant mechanism driving the vertical redistribution of particulate matter. Low frequency storm events and high frequency (daily) sea breezes were found to differ significantly in their retention of particulate matter suspended in the water column. Long periods of calm generally followed the passage of a storm, allowing suspended particulate matter to settle out, while consecutive daily sea breezes were more effective in holding particulate matter in suspension. Linear correlations were found between the backscatter (a proxy for suspended particulate matter), light attenuation and dissolved oxygen concentration. Approximately half the variability in dissolved oxygen concentration could be attributed to the variability in light attenuation, with a decline in concentration during wind resuspension events. Variability in dissolved oxygen concentration was interpreted as a possible indicator of the moderation of pelagic phytoplankton productivity during wind events.     

Trace metals in corals from the Great Barrier Reef

Various octocorallian and scleractinian corals from within the Great Barrier Reef Province were analysed for zinc, copper, cadmium, nickel and lead by atomic absorption spectroscopy. Of the two coral groups, the octocorals accumulated significantly greater amounts of all detectable metals. The soft coral, Sarcophyton sp., revealed distinct inter-locational differences for zinc, copper and cadmium. The potential of this genus for monitoring trace metal pollution in tropical reef waters is briefly discussed.     

Removal fluxes of Mn and Fe from the nearshore waters along the west coast of Taiwan

Dissolved and particulate Mn and Fe in the nearshore waters were determined at 27 stations along the west coast of Taiwan during 19-23 November 2004. The latitudinal distributions of Mn and Fe were very similar; however, the concentration in the dissolved phase was lower, whereas that in the particulate phase was higher in the northern regime. The higher percentage of Fe than Mn that was associated with particles resulted in a two-order of magnitude higher particle-water partition coefficient for Fe, K_d(Fe), than that for Mn, K_d(Mn). The removal fluxes of Mn and Fe could be estimated by multiplying the particulate ²³⁴Th removal flux with the Mn/²³⁴Th and Fe/²³⁴Th ratios in suspended particles, which ranged from 0.1 to 3.8 mmol m⁻² d⁻¹ for Mn, and from 3.4 to 194.5 mmol m⁻² d⁻¹ for Fe. Residence times ranged from 1 to 20 days for Mn and Fe were estimated in the nearshore.     

Dissolved and particulate trace metals in a Scottish sea loch: an example of a pristine environment?

In the near pristine environment of a silled fjord on the west coast of Scotland samples were taken for the determination of dissolved and particulate trace metals (Fe, Mn, Cu, Ni, Cd, Zn and Pb), together with nutrient and hydrographic data, during 19 surveys carried out over a year. An indication of the pristine nature of the environment are the low concentrations of dissolved silicon, phosphate and nitrate which are considerably lower than those of coastal waters which are subject to larger anthropogenic burdens. Distributions of dissolved Cu, Ni and Cd were found to broadly reflect conservative mixing of freshwater and seawater with both end members having similar concentrations. The concentration of dissolved Cu and Ni in seawater entering upper Loch Linnhe (Cu 0.28 μg l⁻¹; Ni 0.26 μg l⁻¹) was consistent with the 1:1 conservative mix of Irish Sea water and North Atlantic surface water predicted from radio-caesium tracer experiments (Mackay & Baxter, 1985). Atmospheric input of trace metals to upper Loch Linnhe appeared to be a relatively minor term in the mass balance relative to fluvial inputs. Values of distribution coefficients Kd were similar to those previously reported for the coastal environment. Iron showed the strongest affinity for the suspended sediments; with particulate percentages of the total load usually greater than 80%. Lead and Mn showed a similar strong affinity to the particle phase. For Cu, Ni and Zn the mass of the element in the dissolved phase was generally greater than that in the particulate fraction. Cadmium, was least associated with the particles, with typically greater than 90% existing in the dissolved phase.     

Particulate and soluble210Pb activities in the deep sea

Particulate and soluble,²¹⁰Pb activities have been measured by filtration of large-volume water samples at two stations in the South Atlantic. Particulate phase²¹⁰Pb (caught by a 0.4-μm filter) varies from 0.3% of total²¹⁰Pb in equatorial surface water to 15% in the bottom water. The “absolute activity” of²¹⁰Pb per unit mass of particulate matter is about 10⁷ times the activity of soluble²¹⁰Pb per unit mass of water, but because the mass ratio of particulate matter to water is about 10^?8, the particulate phase carries only about 10% of the total activity. In Antarctic surface water the particulate phase carries 40% of the total²¹⁰Pb activity; the absolute activity of this material is about the same as in other water masses and the higher fraction is due to the much larger concentration of suspended matter in surface water in this region.In the equatorial Atlantic the particulate phase²¹⁰Pb activity increases with depth, by a factor of 40 from surface to bottom, and by a factor of 4 from the Antarctic Intermediate Water core to the Antarctic Bottom Water. This increase with depth is predicted by our previously proposed particulate scavenging model which indicated a scavenging residence time of 50 years for²¹⁰Pb in the deep sea. A scavenging experiment showed that red clay sediment removes all the²¹⁰Pb from seawater in less than a week. The Antarctic particulate profile shows little or no evidence of scavenging in this region, which may be due to the siliceous nature of the particulate phase in circumpolar waters. Our previous observation that the²¹⁰Pb/²²⁶Ra activity ratio is of the order of 0.5 in the deep water is further confirmed by the two South Atlantic profiles analyzed in the present work.     

Interaction between Scenedesmus obliquus and the Heavy Metals Copper and Lead

The effects of the addition of copper (in copper sulphate and copper chloride) and lead (in lead nitrate and chloride) on Scenedesmus obliquus were studied. The laboratory studies have shown that Sc. obliquus is able to accumulate copper and lead to some extend depending on the concentration of the metal and on the time of contact of algae with the metal. Copper in the concentration of 1 mg/l caused the decrease of the total protein and the growth of the population as well as the destruction of histons, peptids chains and vacuolization of cells. Such drastic effects were observed in the higher concentration of lead (100 mg Pb/l).