Processes affecting particulate trace metals in the sea surface microlayer

Concentrations of particulate Fe, Mn, Ni, Cu, Zn, Cd and Pb have been measured in surface microlayer and subsurface seawater samples collected in the North Sea adjacent to the East Anglian coast, in an area subject to a considerable fluvial input of clay minerals. The results are interpreted by estimating the magnitudes of different processes affecting particulate matter in the microlayer: atmospheric deposition, Brownian diffusion, gravitational settling, bubble flotation and mixing. Both Fe and Mn are strongly depleted in the microlayer, evidently as a result of gravitational settling of Fe- and Mn-bearing mineral particles out of the microlayer. These particles are mixed into the surface region from the water column beneath. Microlayer enrichment of Cu, Zn and Pb was also observed and probably results from flotation of particles attached to rising bubbles. In one set of samples, however, the marked enrichment of these elements, as well as Ni, may result instead from deposition of particles from the atmosphere directly onto the water surface.     

Removal of trace metals from seawater during a phytoplankton bloom as studied with sediment traps in Funka Bay,Japan

To study biological effects on the particulate removal of chemical elements from seawater, sediment trap experiments were carried out successively ten times throughout the spring phytoplankton bloom in Funka Bay. Sediment traps were deployed every one to two weeks at 1, 40 and 80 m depths. The settling particles obtained were analyzed for trace metals, phosphate and silicate. The propagation of diatoms in spring results in larger particulate fluxes than that of dinoflagellates. The biogenic silicate concentration is higher in the earlier period, when diatoms are predominant, than in the subsequent period, when dinoflagellates are predominant. The concentrations of aluminum, iron, manganese and cobalt in the settling particles comprising largely biogenic particles are lower during phytoplankton bloom. The concentration of copper is not reduced by the addition of biogenic particles, and its vertical flux is approximately proportional to the total flux, indicating that its concentration in the biogenic particles is nearly equal to that in the non-biogenic particles. The results for nickel and lead show the same tendency as for copper. Cadmium is more concentrated in biogenic particles than in non-biogenic particles, and the concentration of cadmium in the settling particles decreases with depth, similarly to phosphate and organic matter. Thus, metals in seawater are segregated by biological affinities, and the degree of incorporation into biogenic particles is in the order Cd > Pb, Ni, Cu > Co > Mn, Fe, Al. Biogenic particles are the most important agent controlling the vertical distribution of metals in the ocean. They remove the metals from the surface water, transport them through the water column, and regenerate them in the deep.     

珠江口水域微表层中的痕量金属

采用自制滚筒式自动采样器采样，研究了珠江口水域微表层中Ｆｅ，Ｍｎ，Ｃｕ，Ｐｂ，Ｚｎ，Ｃｄ的含量、分布变化及富集状况。并通过颗粒痕量金属／颗粒Ｆｅ比值计算，探讨了痕量金属的来源。结果表明：Ｃｕ，Ｐｂ，Ｚｎ，Ｃｄ在微表层的平均富集系数分别为２．３，１．４，３．０和１．９。颗粒态Ｆｅ，Ｍｎ的平均富集系数为１．１和０．９。各种金属有明显的季节和空间变化，有各种不同的来源。     

Geochemistry of suspended matter from the Baltic Sea 2. Results of bulk trace metal analysis by AAS

In 1984, on a transect covering the whole Baltic Sea and parts of the adjacent North Sea, 160 water samples were taken and analysed for their concentrations of particulate and dissolved metals. In addition, the suspended materials were investigated for their elemental bulk composition.The particulate fractions represented from about 5% (Cd, Cu and Ni) to 50% (Fe and Pb) of the total (particulate plus dissolved) concentrations. For some elements (Ba, Cd, Cu, Pb and Zn), the particulate matter from the surface microlayer was enriched with respect to those suspended materials taken from 0.2 m depth. This could reflect the atmospheric input of metal-rich aerosols. In anoxic deep waters, maximum contents of Zn (6400 μg g⁻¹), Cu (1330 μg g⁻¹) and Cd (12 μg g⁻¹) were observed in the particulate matter, indicating sulphidic forms. On the other hand, under oxic conditions the distribution coefficients (K_d) decreased with the water depth (Cd, Fe and Pb).Relative to global background levels, the particulate matter contained metal “excesses” amounting to more than 90% of the total contents (Cd, Mn, Pb and Zn). Automated electron probe X-ray microanalysis (EPXMA) revealed that the elemental composition of sediments is mainly governed by post-depositional processes of early diagenesis and is only weakly related to the composition of suspended matter in the overlying water body. For instance, in relation to surface mud sediments of the central Baltic net-sedimentation basins, Zn, Cd, Cu and Mn had 30–100% higher levels in the suspended materials. The general pattern of metal contents of particulate matter taken from 10 m depth on a transect between the Bothnian Bay and the North Sea were—possibly as a result of anthropogenic inputs—rather similar for Pb, Zn and Cu. For Fe and Mn, the distribution patterns along the transect were probably governed by the natural loading characteristics and by the biogeochemistry of those elements.     

Trace metals in seawater and copepods in the ocean outfall area off the northern Taiwan coast

The distribution, partitioning and concentrations of trace metals (Cd, Cr, Cu, Fe, Mn, Pb and Zn) in seawater, including dissolved and particulate phases, and in copepods in the ocean outfall area off the northern coast of Taiwan were investigated. Normalization of metal concentrations to the background metal concentration to yield relative enrichment factors (EF), which were used to evaluate the contamination of dissolved and particulate trace metals in seawater around the ocean outfall. The EF results indicated that the outfall area was significantly contaminated by dissolved Fe and Zn, and by particulate Fe, Cr, Cu, Pb and Zn. In addition, most trace metals were chiefly in the particulate phase. The average percentage of total metal concentrations (dissolved plus particulate phases) bound by suspended particulate matter followed the sequence Al(95%) = Mn(95%) > Pb(88%) > Cu(86%) > Fe(72%) > Zn(32%) > Cr(17.5%) > Cd(3.4%). Therefore, metal contamination is better evaluated in solid phase than in the dissolved phase. The concentration ranges of trace metals in the copepods, Temora turbinata, Oncaea venusta and Euchaeta rimana, near the outfall were: Cd, 0.23-1.81 microg g(-1); Cr, 16.5-195 microg g(-1); Cu, 14-160 microg g(-1); Fe, 256-7255 microg g(-1); Mn, 5.5-80.8 microg g(-1); Pb, 2.6-56.2 microg g(-1); Zn, 132-3891 microg g(-1); and Al, 0.21-1.13%. Aluminum, and probably Fe, seemed to be the major elements in copepods. The concentrations of trace metals in copepods, especially Temora turbinata, near the outfall were generally higher than those obtained in the background station. The mean increase in bioconcentration factor of metals in copepods ranged from 4 to 7 and followed the sequence Al(6.4) > Cu(6.2) > Fe(6.0) > Zn(5.7) > Pb(5.6) > Cr(5.5) > Cd(5.1) > Mn(4.7). Therefore, marine copepods in the waters of northern Taiwan can accumulate trace metals over background concentrations and act as contamination indicators.     

九龙江口和厦门西港海域若干重金属元素的生物地球化学特性

根据１９８７年３月至１９８８年１２月九龙江口，厦门西港海域的调查资料，初步探讨该海域Ｆｅ，Ｍｎ，Ｃｕ，Ｚｎ，Ｎｉ，Ｃｏ，Ｐｂ，Ｃｄ等重金属元素的生物地球化学特性，及其与磷的生物地球化学的关系。结果表明该海域重金属元素的分布主要受九龙江径流的影响。在河水与海水混合过程中，悬浮颗粒态重金属元素发生明显转移，Ｆｅ，Ｍｎ，Ｃｏ，Ｚｎ等元素自悬浮颗粒物上解吸，Ｃｕ可能被吸附，颗粒态重金属元素与颗粒态磷呈良好     

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.     

Trace metal concentrations in the Ross Sea and their relationship with nutrients and phytoplankton growth

Dissolved and particulate trace metal concentrations (dissolved Fe, Zn, Cd, Co, Cu and Ni; particulate Fe, Mn and Al) were measured along two transects in the Ross Sea during austral summer of 1990. Total Fe concentrations in southern Ross Sea and inshore waters were elevated >3.5 times that of northern waters. Dissolved Zn, Cd and Co concentrations were lower by factors of 4.5, 3.5 and 1.6 in southern surface waters relative to northern waters. Dissolved Cu and Ni concentrations were similar in both areas. Elevated Fe concentrations coincided with areas of increased productivity, phytoplankton biomass and nutrient drawdown, indicating that Fe is an important factor controlling the location of phytoplankton blooms in the Ross Sea. Particulate concentrations of Fe, Mn and Al indicate two possible sources of iron to the Ross Sea, resuspension of continental shelf sediments and iron incorporated in annual sea ice and released with meltwaters.     

Budgets of Mn,Cd and Cu in the macrotidal Gironde estuary (SW France)

The behavior and budget of Mn, Cd and Cu in the Gironde estuary were investigated through data from both the water column (WC) and sediment depth profiles. In the estuarine freshwater reaches, Mn and Cd removal from and Cu addition to the dissolved phase occurs with a magnitude equivalent to 10%, 30% and 25% of their respective annual fluvial gross dissolved input, respectively. In the saline estuary, diffusive benthic outflow is the main source of dissolved Mn (74% of the total gross dissolved input within the estuary) to the WC. In contrast, Cd (96%) and Cu (89%) are mainly released into the dissolved phase of the WC from fluvial, estuarine and dredging-related particles through complexation (Cd) and organic carbon mineralization (Cu). Anthropogenic activities (sediment dredging) induce pore water inputs, particulate sulfide oxidation and sediment resuspension, significantly contributing to the metal budget of the WC. The related amounts of metals released could be equivalent to 20–50% (Cd) and up to 70% (Cu) of their respective net dissolved addition. Mass balances suggest that a large part of the metals previously released into the dissolved phase from processes within the estuary are removed by suspended particles due to (co-)precipitation of Fe/Mn (oxy)hydroxides and scavenging on autochthonous organic matter. On an annual basis, the Gironde estuary acts as a net sink of dissolved Mn, removing 60% of the dissolved fluvial inputs, and as a net source of dissolved Cd and Cu, contributing ∼ 85% and 20–45% to the dissolved Cd and Cu fluxes to the ocean.     

Evidence for the decoupling of dissolved, particulate and surface microlayer hydrocarbons in Northwestern Atlantic continental shelf waters

Detailed sampling of the water column and subsequent high-resolution gas chromatographic analyses of surface film, particulate and dissolved hydrocarbons from the Georges Bank region off the New England coast have revealed large spatial and temporal heterogeneity in the source of hydrocarbons. Dissolved hydrocarbons, largely of a petroleum-related origin, surface film hydrocarbon also of a petroleum-related origin but different from the dissolved fraction, and bulk-water particulate matter of a mixed biogenic and petrogenic origin are all decoupled with respect to source and quantity in the region.Surface film (microlayer) hydrocarbons are found in greater concentrations than the dissolved fraction, which in turn is greater than the particulate hydrocarbon quantities in the water column. Although the microlayer appears enriched in hydrocarbons relative to the bulk water, the nature of the hydrocarbons is quite different, indicating that the use of a microlayer enrichment factor may not be appropriate in these waters.     

The distribution and flux of particulate matter in the Bideford River Estuary,Prince Edward Island,Canada

The temporal and spatial distribution of total and organic particulate matter is investigated in the Bideford River estuary. Particulate matter is homogenously distributed in both the water column and the surface sediment, due to high rates of resuspension and lateral transport. The measured mean sedimentation rate for the estuary is 183·5 g of particulate matter m^?2 day^?1, of which more than half is due to resuspension.The surface sediment of the estuary is quantitatively the dominant reservoir of organic matter, with an average of 902·5 g of particulate organic carbon (POC) m^?2 and 119·5 g of particulate organic nitrogen (PON) m^?2. Per unit surface area, the sediment contains 450 times more POC and 400 times more PON than the water column. Terrestrial erosion contributes high levels of particulate matter, both organic and inorganic, to the estuary from the surrounding watershed. Low rates of sediment export from the estuary result in the accumulation of the terrigenous material. The allochthonous input of terrigenous organic matter masks any relationship between the indigenous plant biomass and the organic matter.In the water column, a direct correlation exists between the organic matter, i.e. POC and PON, concentration and the phytoplankton biomass as measured by the plant pigments. Resuspension is responsible for the residual organic matter in the water column unaccounted for by the phytoplankton biomass.The particulate content of the water column and the surface sediment of the estuary is compared to that of the adjacent bay. Water-borne particulate matter is exported from the estuary to the bay, so that no significant differences in concentration are noted. The estuarine sediment, however, is five to six times richer in organic and silt-clay content than the bay sediment. Since sediment flux out of the estuary is restricted, the allochthonous contribution of terrigenous particulate matter to the bay sediment is minor, and the organic content of the bay sediment is directly correlated to the autochthonous plant biomass.     

The geochemistry of deepwater particulate matter over the hydrothermal field at 9°d50′ N (the East Pacific Rise)

The results of geochemical studies of particulate matter in the water mass over the hydrothermal field at 9°50′ N on the East Pacific Rise are presented. The particulate matter was tested in background waters, in the buoyant plume, and in the near-bottom waters. The contents of Si, Al, P, C_org, Fe, Mn, Cu, Zn, Ni, Co, As, Cr, Cd, Pb, Ag, and Hg were determined. No definite correlations were found between the ele-ments in the background waters. Many of the chemical elements correlated with Fe and associated with its oxyhydroxides in the buoyant plume. In the near-bottom waters, microelements are associated with Fe, Zn, and Cu (probably, to their sulfides formed under fluid mixing with seawater). The matter precipitated in a sed-imentation trap was similar to the near-bottom particulate matter in the elemental composition.     

Spatial and temporal distribution of Fe, Ni, Cu and Pb along 140°E in the Southern Ocean during austral summer 2001/02

The distribution of dissolved (D) and acid-dissolvable (AD) Fe, Ni, Cu and Pb in the upper water column (0–300 m depth) was determined in the Australian sector of the Southern Ocean (140°E meridian) during three cruises conducted between November 2001 and March 2002. For Ni and Cu, there was no significant difference in concentration between dissolved and acid-dissolvable species. DNi and DCu showed significant (P = 0.01) positive correlations with silicate, phosphate and nitrate, reflecting their strong nutrient-type behaviour. For Fe and Pb, the acid-dissolvable concentration mostly exceeded the dissolved concentration, reflecting the importance of labile particulate species for these elements. DPb decreased between January and February in the Polar Frontal Zone and in Antarctic continental shelf water. ADPb maxima occurred in the Antarctic Zone, resulting in a maximum AD/D ratio of 7. The mean DFe concentration in the surface mixed layer was 0.3 nM in the sub-Antarctic zone, 0.4 nM in the Polar Frontal Zone, 0.5 nM in the Antarctic Zone and increased southward beyond the Antarctic Divergence and towards the continent. DFe did not show a clear temporal change in its horizontal distribution, which was in contrast to the other nutrients and trace metals. ADFe substantially increased in Antarctic continental shelf water where the AD/D ratio reached 11. The following conclusions can be drawn from these data. (1) Ni and Cu exist exclusively as dissolved species and their distributions are mainly controlled by their biogeochemical cycling, similar to those of the major nutrients. (2) Pb is dominated by particulate species. The distribution of DPb is temporally and spatially variable due to a sporadic source and strong scavenging. (3) DFe is rather a minor fraction of total Fe in Antarctic continental shelf water where shelf sediments and Antarctic sea-ice appear to be strong sources for Fe. There is substantial temporal variation in the supply of Fe to the upper water column. DFe in the mixed layer of the open Southern Ocean is maintained at low concentrations throughout summer due to uptake by phytoplankton and scavenging.     

Composition of the inorganic fraction of the particulate organic matter in seawater

Na, K, Mg, Ca, Fe, and Mn have been measured in both naturally occurring particulate matter and artificially created aggregates taken from water from the Nova Scotian coastal region and from the North Atlantic Ocean. The order of concentration of these elements is the same in both the aggregates and the natural particulate matter as it is in seawater. There is an inverse relationship between depth of the water and the amount of inorganic matter in artificially created aggregates, while a direct relationship is found with the naturally occurring particles. This direct relationship may reflect the utilization of organic material in the surface waters. Iron and manganese are enriched in both kinds of particles.     

Some peculiarities of the trace-metal distribution in Baltic waters and sediments

Between 1980 and 1984 extensive studies were carried out in the Baltic Sea on trace metals (Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in water, suspended matter and sediments. The results enabled the influence of different factors on metal distribution patterns to be considered. The vertical profiles of dissolved and particulate metals in waters of the central deep basins reflect influences caused by oxygen deficiency and anoxic conditions in near-bottom water layers. Peculiarities at Station BY15 in the Gotland Deep included high dissolved Fe, Mn and Co concentrations and remarkable enrichment of Zn (0.64%), Cd (51 μg g⁻¹) and Cu (0.15%) in particulate matter from the anoxic zone. Manganese-rich particles were accumulated above this layer.In fine-grained soft sediments below anoxic deep waters, maximum contents of Cd, Cu and Zn were observed, relative to other coring sites, between Bothnian Bay and Lübeck Bight. The Hg content in sediments probably reflects the joint flocculation with organic matter. Land-based sources seem to play the leading part for maximum lead contents.     

Dissolved and particulate heavy metals distribution in coastal lagoons. A case study from Mar Chiquita Lagoon,Argentina

Mar Chiquita Coastal Lagoon is located on the Atlantic coast of Argentina, and it has been declared a Biosphere Reserve under the UNESCO Man and Biosphere Programme (MAB). This coastal lagoon constitutes an estuarine environment with a very particular behaviour and it is ecologically important due to its biological diversity. The aim of the present study was to evaluate the distribution and geochemical behaviour of several heavy metals in this coastal system, focusing on their distribution in both the dissolved phase (<0.45 μm) and the suspended particulate matter. Therefore, the general hydrochemical parameters (salinity, temperature, turbidity, pH and dissolved oxygen) and concentration of total particulate and dissolved metals (Cd, Cu, Ni, Zn, Fe, Pb, Cr and Mn) were measured along 2 years (2004–2006) at two different sites. As regards their distribution, hydrological parameters did not present any evidence of deviation with respect to historical values. Suspended particulate matter showed no seasonal variation or any relationship with the tide, thus indicating that in this shallow coastal lagoon neither tides nor freshwater sources regulate the particulate matter input. Heavy metals behaviour, both in dissolved and particulate phases did not reveal any relationship with tide or seasons. Mar Chiquita Coastal Lagoon showed a large input of dissolved and particulate metals, which is probably due to intensive agriculture within the drainage basin of this system.     

A study of the geochemistry of suspended particulate matter in coastal waters

The concentrations of Si, Al, Ti, Fe, K, Ca, Mg, P and Mn, before and after chemical leaching, in particulate matter from waters off the west coast of Scotland have been measured in vertical profiles at two seasons. The distribution of Si and Ca are shown partly to reflect temporal changes in biological production in different waters. The distributions of Al, Ti, Fe, K and Mg have been used to distinguish different sources and types of suspended alumino-silicates, and to trace probable circulation patterns in the water mass.While Si and Ti contents of the particulate matter are unaffected by mild chemical leaching, large amounts of other elements, notably Mg, K and Al, can be removed by this treatment. Presumably, these losses indicate preferential release of these elements from octahedral and interlayer sites in clay mineral lattices.The distribution of particulate P covaries with non-silicate Fe in the surface waters, while in bottom waters, high concentrations of particulate Fe and Mn are associated. The relationship of Fe and P is considered to be due to the presence of particulate ferriphosphates derived from runoff. The particulate Mn and Fe in deep waters is produced by the precipitation of dissolved metals released from bottom sediments by diagenesis.     

Stoichiometry among bioactive trace metals in the Chukchi and Beaufort Seas

The distribution of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in seawater was investigated in the Chukchi and Beaufort Seas of the western Arctic Ocean in September 2000. The unfiltered and filtered seawater samples were used for determination of total dissolvable metal (TDM) and dissolved metal (DM), respectively. The concentration of labile particulate metal (LPM) was estimated with the difference between that of TDM and DM. The concentrations of TDAl, TDMn, TDFe, TDCo and TDPb varied substantially in the study area. The high concentrations occurred at stations near the Bering Strait, in the Mackenzie delta, and above reductive sediments on the shelf and slope. These elements were mostly dominated by labile particulate species, such as Fe?CMn oxides and species adsorbed on terrestrial clay. DCo was correlated with DMn over the study area (r?=?0.78, n?=?135), and the slope of the regression line was 27 times higher at a pelagic station than at a shelf station. TDNi, TDCu, TDZn and TDCd showed relatively small variations and were generally dominated by dissolved species. There was a moderate correlation between DCd and phosphate for all samples (r?=?0.79), whereas there were no significant correlation between the other DMs and nutrients. TDNi and TDCu showed a remarkable linearity for most stations except those near the Bering Strait (R ²?=?0.95, n?=?126). These results suggest that biogeochemical cycling including uptake by phytoplankton and remineralization from settling particles has only minor control over the distribution of trace metals in this area. Using the present data, the annual input of bioactive trace metals form the Bering Strait and the Mackenzie River was estimated. Also, the trace metal compositions of major water masses were evaluated. The dissolved elemental ratio was P:Al:Mn:Fe:Co:Ni:Cu:Zn:Cd?=?1:1.2?×?10^?2:4.4?×?10^?4:1.4?×?10^?3:3.7?×?10^?5:3.7?×?10^?3:1.4?×?10^?3:4.5?×?10^?3:2.2?×?10^?4 for Canada Basin deep water (CBDW). This ratio was significantly different from that for Pacific deep water and Bering Sea water, suggesting substantial modification of the trace metal compositions of seawater in the study area.     

Concentrations of suspended matter and particulate cadmium,copper, lead and zinc in the Indian sector of the antarctic ocean

The concentrations of suspended matter and particulate Cd, Cu, Pb and Zn were determined for 36 samples collected at 6 stations in the Antarctic Ocean during December, 1970 and January, 1971 using membrane filters. The concentration of suspended matter was determined gravimetrically and trace metal levels were determined using anodic stripping voltammetry. For waters deeper than 100 m the concentration of suspended matter was < 100 μg l^?1. Concentrations up to 542 μg l^?1 were recorded between surface and 100 m. Individual concentrations of the metals were scattered with depth. Average concentrations of particulate metals were: Cd, 3.5 ng l^?1; Cu, 100 ng l^?1; Pb, 35 ng l^?1; and Zn, 230 ng ;l^?1 These measurements represent non-steady state conditions of early Antarctic summer as the ice pack disintegrates and biological activity increases.     

Contrasting behaviour of trace metals in the Scheldt estuary in 1978 compared to recent years

Dissolved and particulate trace metals (Cu, Cd, Pb, Zn, Ni, Fe and Mn) measured at six stations along the Scheldt estuary in October/November 1978 are compared with more recent data. Based on Ca content in the suspended matter, three distinct geochemical regions could be distinguished: the upper estuary (salinity 1–7) dominated by fluvial mud, mid-estuary (salinity 7–17) where the composition of the suspended matter remained relatively constant, and the lower estuary where marine mud prevailed. Re-suspension of sediments is the major factor controlling the composition of the particles in the upstream region. Anoxic conditions prevailed in the upper part of the estuary extending to a salinity of 15 in 1978, while at present the seaward boundary of the anoxic water body is located at less saline waters. Furthermore, the present-day metal load is much lower than in 1978. As a consequence of the changed situation, maxima in dissolved concentrations of redox-sensitive metals in the mid/lower estuary have moved as well, which affects the trace metal re-distribution pattern. In the anoxic zone, exchange processes between dissolved and particulate metal fractions were strongly redox regulated, with Fe and Mn as excellent examples. Iron was removed from the dissolved phase in the early stages of mixing resulting in an increase in the suspended particulate matter of the leachable ‘non-residual' Fe fraction from 2 to 3.5%. Due to its slower kinetics, removal of Mn from solution occurred in mid-estuary where oxygen concentrations increased. Cu, Cd and Zn on the contrary were mobilised from the suspended particles during estuarine mixing. External inputs of Pb, and to a lesser extent of Cu, in the lower estuary resulted in the increase of their particulate and the dissolved concentrations. Calculated K_d (distribution coefficient) values were used to assess the redistribution between the dissolved and particulate phase of the investigated metals. Due to the existence of the anoxic water body in the upper estuary, the importance of redox processes in determining the K_d values could be demonstrated. The sequence of K_d values in the upper estuary (Fe, Cd, Zn, Pb > Cu > Ni, Mn) is significantly different from that in the lower estuary (Fe > Mn > Pb, Ni, Zn, Cu, Cd). Thus, in such a dynamic estuary single metal-specific K_d values cannot be used to describe redistribution processes.