Copper, lead and cadmium in coastal waters of the western North Sea

Cadmium, lead and copper have been determined in both dissolved and particulate phases for 130 surface-water samples from the coastal zone of Scotland and England in the western North Sea. The concentrations reported are, in general, lower than those published previously for the same area.The distribution of total metal concentration between the dissolved and particulate phases varies for the three elements. The lead distribution is dominated by its associations with particulate material while cadmium shows the reverse behaviour, existing almost totally in the dissolved phase. Copper is intermediate in behaviour, with the dissolved phase generally being dominant.An inverse relationship between salinity and dissolved copper concentration suggests a freshwater origin for this element. It is suggested that sedimentary and/or anthropogenic sources affect dissolved copper concentrations in coastal waters. The dissolved lead distribution reveals plumes of contaminated coastal water. The lead distribution is, however, dominated by associations with particulate material and sediments which produce a sharp concentration gradient close to the coast. The Humber estuary is identified as a significant source of cadmium to the North Sea.     

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Cadmium, lead and copper have been determined in both dissolved and particulate phases for 130 surface-water samples from the coastal zone of Scotland and England in the western North Sea. The concentrations reported are, in general, lower than those published previously for the same area.The distribution of total metal concentration between the dissolved and particulate phases varies for the three elements. The lead distribution is dominated by its associations with particulate material while cadmium shows the reverse behaviour, existing almost totally in the dissolved phase. Copper is intermediate in behaviour, with the dissolved phase generally being dominant.An inverse relationship between salinity and dissolved copper concentration suggests a freshwater origin for this element. It is suggested that sedimentary and/or anthropogenic sources affect dissolved copper concentrations in coastal waters. The dissolved lead distribution reveals plumes of contaminated coastal water. The lead distribution is, however, dominated by associations with particulate material and sediments which produce a sharp concentration gradient close to the coast. The Humber estuary is identified as a significant source of cadmium to the North Sea.     

Atmospheric transport and input of hydrocarbons to the subtropical North Atlantic

Seawater samples and airborne particulate material were collected in the subtropical North Atlantic during R.V. “Meteor” Cruise M60 (N34°47.2′W26°57.7′/N10°1.3′W32°58.3′). Hydrocarbon concentrations were estimated in the samples. For seawater the concentrations ranged from 0.2 μg to 3.5 μg dm⁻³. In the open ocean air the concentrations of the particulate hydrocarbon measured at 14m above sea level ranged from 2.8 ng to 133.1 ng m⁻³. A significant increase was observed during a Saharan dust outbreak. Comparison with aluminium concentrations in seawater and in the air suggests input of atmospheric hydrocarbons by dry deposition to be an important transportation pathway.     

Metal fluxes through the Strait of Gibraltar: the influence of the Tinto and Odiel rivers (SW Spain)

A large set of new data concerning dissolved metal concentrations has been acquired in the Gulf of Cadiz and in the Strait of Gibraltar from 1996 to 1999. These data, associated with models (hydrodynamic, tracer advection–dispersion and mixing), have been used to assess the influence of rivers draining the South Iberian Pyrite Belt on the Gulf of Cadiz and on the Atlantic inflow in the Strait of Gibraltar.Metal concentrations in surface waters from the Gulf of Cadiz are maximal near the mouth of the Tinto/Odiel rivers with values exceeding 50 nmol/kg (Mn), 5 nmol/kg (Ni), 30 nmol/kg (Cu), 100 nmol/kg (Zn), 0.9 nmol/kg (Cd) and 45 nmol/kg (As). From the Tinto/Odiel river, a plume of contamination follows the coast in the direction of the Strait of Gibraltar. The computation of a tracer advection–dispersion model confirms that the coastal currents carry the metals discharged from the Tinto and Odiel to the Strait of Gibraltar.From temperature–salinity and metal–salinity plots, four water masses can be recognised in the Gulf of Cadiz and in the Strait of Gibraltar: North Atlantic Surface Water (NASW), North Atlantic Central Water (NACW) and metal-enriched Spanish Shelf Waters from the Gulf of Cadiz (SSW). The Mediterranean Outflow Water (MOW) is also clearly seen at depths greater than 300 m.The chemical characteristics of these various water masses have been used in a mixing model to evaluate their relative contribution to the Atlantic inflow through the Strait of Gibraltar. These contributions are seasonally variable. In June 1997, the contribution was: 80±20%, 5±5% and 15±10% for NASW, NACW and SSW, respectively. In September, the SSW contribution was apparently negligible.Finally, these relative contributions allow the evaluation of the metal fluxes in the Strait of Gibraltar. The presence of SSW in the Strait increases the metal flux to the Mediterranean Sea by a factor of 2.3 (Cu), 2.4 (Cd), 3 (Zn) and 7 (Mn). It does not modify significantly As and Ni fluxes.     

The clay mineralogy of particulate material from some surface seawaters of the eastern Atlantic Ocean

The concentrations of the clay minerals montmorillonite and illite have been determined in 28 samples of particulate material from surface (0–～5 m) waters along the eastern margins of the Atlantic Ocean, and the concentrations of chlorite and kaolinite have been determined in nineteen of the samples.The average concentration of the four clays in the particulate material decreases in the following order: illite (～42%) > kaolinite (～25%) > chlorite (～19%) > montmorillonite (～14%). There are specific trends in the latitudinal distributions of illite and kaolinite in the particulate material; illite decreases and kaolinite increases towards low latitudes. These trends are also found in eolian dusts and deep-sea sediments from the same region, and these clays are considered to have a detrital origin.The concentrations of montmorillonite in the particulate material and deep-sea sediments are similar in the North Atlantic. However, in the South Atlantic the sediments contain about twice as much montmorillonite as does the particulate material. It is suggested that whereas the montmorillonite in North Atlantic deep-sea sediments is largely detrital, that in South Atlantic sediments is both detrital and authigenic.     

Molecular weight distribution of dissolved organic materials in seawater determined by ultrafiltration: a re-examination

Most of the dissolved organic materials (DOM) in coastal Maine, Gulf of Maine, and North Atlantic seawaters had molecular weights (MW), determined by ultrafiltration, less than 1000. Only 34% of the DOM had MW greater than 1000, only 6% had MW greater than 30 000, and only 1% was of MW greater than 100 000. The majority of ultrafilter-derived MW data are consistent with patterns shown here; earlier reports of high-MW DOM in seawater were apparently exaggerated due to procedural and ultrafilter artifacts. It is also shown that most ultrafiltration data do not clearly indicate loss of high-MW DOM during estuarine mixing, and that apparent removal could result from decreased retention as ionic strength increases.     

Variations in the chemical lability of iron in estuarine, coastal and shelf waters and its implications for phytoplankton

The relationship between total and chemically labile Fe has been studied in estuarine, coastal and shelf waters of the Gulf of Maine, U.S.A. Measurements of the labile fraction of total Fe, defined by complexation with 8-hydroxyquinoline in 1 h, correlate with the availability of Fe to marine phytoplankton and therefore can be used to estimate Fe availability in seawater. The results show that the relative lability (=labile/total) of Fe in seawater varied both spatially and temporally from near-zero to 100%. Although particulate Fe (>0.45 μm) was generally less labile than dissolved Fe (<0.45 μm), the particulate fraction often contributed substantially to labile Fe concentrations overall. Conversely, as much as 75% of ‘dissolved’ Fe was non-labile, and therefore was probably not available to phytoplankton. In seawater/river-water mixing experiments, aggregation diminished the relative lability of Fe by 30%, even though much of it remained in the ‘dissolved’ fraction. Considering phytoplankton nutrition, these results demonstrate that equating dissolved Fe concentrations with ‘available’ metal can be misleading. Furthermore, the large variability observed in the labile proportion of total Fe in seawater indicates that Fe availability to phytoplankton cannot be estimated by applying fixed lability-ratios to total Fe concentrations.     

Organic carbon and nitrogen in the northern California current system: comparison of offshore, river plume, and coastally upwelled waters

During the first year of the Northeast Pacific GLOBEC program we examined the spatial distributions of dissolved and particulate organic carbon and nitrogen in the surface waters off the Oregon and Washington coasts of North America. Eleven east–west transects were sampled from nearshore waters to 190 km offshore. Hydrographic data and the distribution of inorganic nutrients were used to characterize three distinct water sources: oligotrophic offshore water, the Columbia River plume, and the coastal upwelling region inshore of the California Current. Warm, high salinity offshore water had very low levels of inorganic nutrients, particulate organic carbon (POC) and dissolved organic carbon (DOC). Warm, low salinity water in the Columbia River plume was relatively low in nitrate, but showed a strong negative correlation between salinity and silicate. The river plume water had the highest levels of total organic carbon (TOC) (up to 180 μM) and DOC (up to 150 μM) observed anywhere in the sampling area. Cold, high salinity coastal waters had high nutrient levels, moderate to high levels of POC and particulate organic nitrogen (PON), and low to moderate levels of DOC and dissolved organic nitrogen (DON). Each of these regions has characteristic C:N ratios for particulate and dissolved organic material. The results are compared to concentrations and partitioning of particulate and dissolved organic carbon and nitrogen in other regions of the North Pacific and North Atlantic Oceans.     

Chemical fractionation of zinc versus cadmium among other metals nickel, copper and lead in the northern North Sea

Concentrations of dissolved Ni, Cu, Zn, Cd and Pb were measured in water samples collected during a cruise with R.V Pelagia (29-6/14-7-1993) in the northern North Sea and N.E. Atlantic Ocean. At least six depths (0–90 m) were sampled with modified Go-Flo samplers from a rubber zodiac. In the study area, the first 25 m were well mixed and stratification occurred below this depth. The local bloom of Emiliania huxleyi hardly affected the trace metals concentration, except for some removal of Cd as seen from its correlation with nitrate. The mean dissolved concentrations were for Ni (3.66 nM), Cu (1.61 nM), Zn (4.5 nM), Cd (48 pM) and Pb (108 pM). These concentrations are among the lowest reported for the North Sea and are of similar magnitude to those found in the eastern North Atlantic at the same latitude. Zn was the only exception with values 10 times higher compared to those in the Atlantic Ocean, suggesting external inputs, mainly atmospheric and possibly from surrounding land masses. The observed ratio Zn:Cd in the North Sea and estuaries is in between the high ratio 600–900 for continental sources and the low ratio 5–10 for oceanic waters. Latter low ratio is consistent with the 21-fold stronger inorganic complexation of Cd in seawater which, in combination with the preferential biological uptake of Zn, may lead to the observed about hundredfold fractionation of Zn versus Cd in the marine system. Other processes may play a role but would need further investigation. The dissolved Pb values tend to be lower than found before in the North Sea, indicating decreasing inventories due to reduced anthropogenic emissions.     

Trans-Atlantic responses of Calanus finmarchicus populations to basin-scale forcing associated with the North Atlantic Oscillation

Populations of the copepod species Calanus finmarchicus often dominate the springtime biomass and secondary production of shelf ecosystems throughout the North Atlantic Ocean. Recently, it has been hypothesised that interannual to interdecadal fluctuations observed in such populations are driven primarily by climate-associated changes in ocean circulation. Here, we compare evidence from the North Sea and Gulf of Maine/Western Scotian Shelf (GoM/WSS) linking fluctuations in C. finmarchicus abundance to changes in ocean circulation associated with the North Atlantic Oscillation (NAO). A particularly striking contrast emerges from this Trans-Atlantic comparison: whereas the North Sea C. finmarchicus population exhibits a negative correlation with the NAO index, the GoM/WSS population exhibits a more complex, positive association with the index. The physical processes underlying these contrasting population responses are discussed in the context of regional- to basin-scale circulation changes associated with the NAO.     

The atmospheric distribution of lead over a number of marine regions

A data base of 111 filter-collected marine atmospheric particulates is used to describe the distribution of lead over the North and South Atlantic, the Mediterranean Sea, the Red Sea, the Gulf of Aden and the northern and central Arabian Sea. The distribution of atmospheric Pb is assessed in terms of enrichment factor diagrams, and it is shown that over the marine regions studied in both the Northern and Southern Hemispheres the distribution of Pb in the atmosphere is controlled by the mixing of a background component, or components, with crustal material within certain concentration limits. For the Northern Hemisphere samples used in the investigation there is a reasonably well-defined Pb concentration minimum of ～ 0.6 ng m^?3 of air; however, this will be severely decreased in more remote Northern Hemisphere marine regions. Geometric average Pb atmospheric concentrations vary from one marine region to another, ranging from ～ 0.98 ng m^?3 of air for the South Atlantic westerlies to ～ 15 ng m^?3 of air in the North Atlantic westerlies; although the latter reduces to ～ 7 ng m^?3 of air when ‘polluted’ samples are excluded. Lead sea-surface deposition fluxes are calculated on the basis of two deposition velocities (0.25 and 1 cm s^?1), the largest flux (220 ng Pb cm^?2 yr^?1) being found for the westerlies over the eastern margins of the North Atlantic. The distribution of lead over the North Atlantic is assessed in terms of the global lead budget and it is estimated that a maximum of ～ 24% of the total ‘natural’ lead injected annually into the World atmosphere, and ～ 3.5% of the anthropogenic lead injected annually into the Northern Hemisphere atmosphere, are deposited over the North Atlantic sea surface.     

Cd, Pb, Cu, Ni and Co distribution in the German Bight

Cd, Pb and Cu concentrations, dissolved and total, have been determined in the German Bight. In 1975, 1977, 1978, 1980 and 1983 water samples were collected at 215 sampling stations. In the 1983 mission samples were also analysed for Ni and Co. The samples were filtered and acidified immediately after collection. Analysis was performed by voltammetry.The analytical data indicate that a net portion of the Cd, the Weser being a distinct source for it, will cross the estuarine zone. Open sea Cd levels in the German Bight are about a factor 10 higher than North Atlantic values. Pb, being transported mainly with the suspended particulate phase (up to 99.5%), is better eliminated by sedimentation in the estuaries. Ni and Cu occur mainly in the dissolved phase. Pollution by Co is distinct in the Elbe, but the output is rapidly diluted to background contents below 10 ng kg⁻¹. An interpretation of the results from the different years yields a rather steady state situation in the German Bight.     

Manganese recycling in coastal waters

Both water and suspended particulate matter in the deep water of the Gulf of St. Lawrence are greatly enriched in manganese. Maximum dissolved manganese concentrations are encountered close to the sediment-water interface whereas the particulate matter with highest manganese content occurs 30–100 m above the bottom. The elevated concentrations are attributed to the diagenetic release of dissolved manganese from the underlying fine-grained sediments and its subsequent precipitation in the water column. The rate of manganese precipitation is rapid compared to the rates of diffusion and mixing in the bottom water. Part of the manganese-enriched particulate matter becomes mixed throughout the water column by advection and diffusion. Thus, particles enriched in manganese can ultimately be carried into the open ocean by prevailing currents. This process, which appears to be widespread in eastern Canadian coastal waters, enables manganese originally associated with rapidly settling terrigenous particles to be transferred to slowly settling fine-grained suspended particles entering the ocean from coastal environments. In this way, riverborne manganese of terrigenous origin may well account for a major proportion of the excess manganese in pelagic sediments.     

The behaviour of dissolved Cd, Co, Zn, and Pb in North Atlantic near-surface waters (30°N/60°W–60°N/2°W)

In September 1993 (M26) and June/July 1996 (M36), a total of 239 surface samples (7 m depth) were collected on two transects across the open Atlantic Ocean (224 samples) and northwest European shelf edge area. We present an overview of the horizontal variability of dissolved Cd, Co, Zn, and Pb in between the northwest and northeast Atlantic Ocean in relation to salinity and the nutrients. Our data show a preferential incorporation of Cd relative to P in the particulate material of the surface ocean when related to previously published parallel measurements on suspended particulate matter from the same cruise. There is a good agreement with results recently estimated from a model by Elderfield and Rickaby (Nature 405 (2000) 305), who predict for the North Atlantic Ocean a best fit for α_Cd/P=[Cd/P]_POM/[Cd/P]_SW of 2.5, whereas the approach of our transect shows a α_Cd/P value of 2.6. The Co concentrations of our transects varied from <5 to 131 pmol kg⁻¹, with the lowest values in the subtropical gyre. There were pronounced elevations in the low-salinity ranges of the northwest Atlantic and towards the European shelf. The Co data are decoupled from the Mn distribution and support the hypothesis of marginal inputs as the dominant source. Zinc varied from a minimum of <0.07 nmol kg⁻¹ to a maximum of 1.2 and 4.8 nmol kg⁻¹ in regions influenced by Labrador shelf or European coastal waters, respectively. In subtropical and northeast Atlantic waters, the average Zn concentration was 0.16 nmol kg⁻¹. Zinc concentrations at nearly three quarters of the stations between 40°N and 60°N were <0.1 nmol kg⁻¹. This suggests that biological factors control Zn concentrations in large areas of the North Atlantic surface waters. The Pb data indicated that significant differences in concentration between the northwest and northeast Atlantic surface waters presently (1996) do not exist for this metal. The transects in 1993 and 1996 exhibited Pb concentrations in the northeast Atlantic surface waters of 30 to 40 pmol kg⁻¹, about a fifth to a quarter of the concentrations observed in 1981. This decline is supported by our particle flux measurements in deep waters of the same region.     

Concentrations of cadmium,copper, lead and zinc in surface waters of the Northwest Atlantic Ocean — A comparison of Go-flo and teflon water samplers

The concentrations of cadmium, copper, lead and zinc were measured at two locations in surface waters of the western North Atlantic. Samples were collected upstream of the research vessel in 1-1 teflon bottles, and in a 30-1 teflon-coated Go-flo bottle. Surface mixed-layer samples were also collected at each location by ship cast using this same Go-flo sampler. A comparison of the three sampling modes shows that all the samples taken with the Go-flo sampler possessed much higher concentrations of zinc (7–10-fold) and lead (2–3-fold) than those collected directly in teflon bottles. No apparent differences were noted at each station in the concentrations of either copper or cadmium among the samples collected by the three different procedures. The measured values for copper and cadmium in these waters are in good agreement with recent reports for the western North Atlantic.     

Variability of the apparent quantum efficiency of CO photoproduction in the Gulf of Maine and Northwest Atlantic

The photochemical oxidation of colored, dissolved organic matter (CDOM) is important for carbon cycling in the ocean. This oxidation process produces a number of products, including carbon monoxide (CO). While the photochemical production efficiency of CO (apparent quantum yield, AQY, defined in terms of CDOM absorbance) has been reported to be similar for many water types, a full evaluation of the observed natural variability in CO AQY requires additional study. Here we use a polychromatic irradiation system to determine twenty AQY spectra at sea on fresh samples ranging from the near coastal waters of the Gulf of Maine to the offshore waters of the Northwest Atlantic. Despite the geographic variability of these marine samples the AQY of CO production in the Gulf of Maine and Northwest Atlantic exhibited only a small degree of variability, none of which was not correlated with measured environmental parameters. Consequently, a single aggregate AQY spectrum _λ = e^{(−(9.134+0.0425(λ−290)))+e(−(11.316+0.0142(λ−290)))} was found to adequately represent the entire data set. Significantly, the accuracy of an AQY spectrum determined using this multispectral/statistical technique was confirmed with data obtained from a monochromatic irradiation technique on a single open ocean sample. Taken together, the AQY spectra determined in this study were similar in magnitude and shape to those previously published for marine samples and, overall, were somewhat lower than those previously reported for freshwater studies.     

Particle flux across the mid-European continental margin

Results are presented from particle flux studies using sediment trap and current meter moorings along a transect at the European continental margin at 49°N within the EU-funded Ocean Margin Exchange (OMEX) project. Two moorings were placed, at the mid- and outer slope in water depths of 1500 and 3660 m, with traps at 600 and 1050 m and at 580, 1440 and 3220 m, respectively. Residual currents at the mid-slope follow the slope contour, whereas seasonal off-slope flow was registered at the outer slope. At 600 m on the slope fluxes are similar to those in the abyssal North Atlantic. The flux of all components (bulk dry weight, particulate organic and inorganic carbon, lithogenic matter and opal) increased with water depth. Highest fluxes were recorded at 1440 m at the outer slope, where off-slope residual currents mediate particle export. The injection of biogenic and lithogenic particles below the depth of winter mixing results in the export of particles from shallower waters. Calculated lateral fluxes of particulate organic carbon exceed the primary flux by over a factor of 2 at 1440 m on the outer slope. Estimated lateral fluxes of suspended particulate matter in the water column and intermediate nepheloid layers at the outer slope are potentially large compared to sinking fluxes measured by sediment traps. A comparison is made of particle flux at three continental margin sites and two sites in the adjacent open North Atlantic, from which it is seen that bulk and organic matter flux increases exponentially with proximity to the shelf break. The percentage contribution of particulate organic carbon to biogenic fluxes increases from a mean of 5.7% in the abyssal N. Atlantic to 13.9% at the continental margins.     

CHROMIUM DISTRIBUTION AND TRANSFER IN SEAWATER OF BOHAI GULF

The concentrations of dissolved chromium in seawater of the Bohai Gulf vary from trace to 1.6 μg /1 while those of particulate chromium from trace to 8.66 μg/1, indicating that the concentration of chromium in seawater of nearshore and estuary in the Bohai Gulf is higher than that of offshore, and reflecting the effects of estuarine and terrestrial pollutions. Observation data indicate that there is a positive correlation between particulate chromium and COD.The result shows that organic matter in seawater has a strong ability to combine chromium. When particulate chromium meets with seawater in estuary, it gradually settles down to sea-bottom sediments. Ratio of particulate chromium to total chromium in the Bohai Gulf yields a higher value, exceeding 90% in estuarine area, i.e. particulate chromium is a predominant form in seawater of the Bohai Gulf.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl^?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl^?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn²⁺ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl^?1, indicating that the oxidation of Fe²⁺ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl^?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters.     

Variations of particulate proteins and dissolved amino acids in coastal seawater

The relationships existing between the protein-containing fraction of particulate matter and amino acids dissolved in seawater were studied in the Gulf of Marseille at different periods of the year. The concentration of particulate proteins was almost zero in February and attained maximum values during April and May, the average concentrations of dissolved amino acids (total) varied between 900 and 1200 nmole l^?1 but larger variations were encountered at the surface and in the vicinity of the sediment. The influence of meteorological conditions and the effect of the sediment on the distribution of nitrogenous substances were taken into account. Combined dissolved amino acids were more abundant than free dissolved amino acids in 90% of the cases. The concentrations of dissolved amino acids observed in a zone bordering the North Mediterranean are comparable to those found in other regions of the world.