Trace metal dynamics in a seasonally anoxic lake

Selected results are presented from a detailed 12-month study of trace metals in a seasonally anoxic lake. Dissolved concentrations of Fe, Mn, organic carbon, Cd, Cu, Pb, Zn, and pH were determined in the water column and the interstitial waters on 39 occasions. Trace metal concentrations remained low throughout the year in both water column and pore waters. There was evidence for some remobilization at the sediment-water interface but sediments deeper than 3 cm acted as a sink throughout the year. Variations in the water concentrations were largely associated with increased loading during periods of heavy rainfall. During the summer, concentrations of Cu and Zn in the waters overlying the sediments were enhanced by release from decomposing algal material. Similarly, enhanced concentrations of Cd, Cu, Pb, and Zn were observed during periods of much reduced mixing during ice-cover. Although there were large seasonal variations in the concentrations of dissolved and particulate Fe and Mn, there were no comparable changes in the concentrations of trace metals.     

Trace metals in oxic lake sediments: possible adsorption onto iron oxyhydroxides

Apparent overall equilibrium constants for the adsorption of Cd, Cu, Ni, Pb and Zn onto natural iron oxyhydroxides have been calculated from the partitioning of these trace metals in oxic lake sediments and the in situ measurement of trace metal concentrations in the associated pore waters. Such values obtained from lakes of various pH located on the Precambrian Shield, in the area of Sudbury, Ontario, are compared with equilibrium constants obtained for the adsorption of the trace metals onto iron oxyhydroxides in well-defined media.The field data are consistent with laboratory experiments reported in the literature and with theory. Both the influence of pH upon adsorption and the binding strength sequence observed for the field data agree with theory. At high sediment pH values, the partitioning of Cd, Ni and Zn between the pore waters and the natural iron oxyhydroxides is similar to those reported in the literature for the adsorption of these metals at low surface coverage onto amorphous iron oxyhydroxides in a NaNO₃ medium; deviation from this simple model is however observed for Cu and Pb, presumably due to the competitive action of dissolved ligands. At low sediment pH values, the adsorption is much higher than predicted by the simple model and can be explained by the formation of ternary complexes with the iron oxyhydroxide surface.     

Enrichment of trace metals in surface sediments from the northern part of Point Calimere, SE coast of India

This study deals with the geochemical nature of distribution, enrichment of total trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) in bulk sediments and its association with sediment texture, carbonates and organic carbon. Sixty surface sediment samples were collected during two different seasons in 2002 and 2003 along the coastal regions in three transects from Nagapattinam town, north of Point Calimere in southeast coast of India. The sediments are mostly sandy silt and are dominated by the carbonate content. Organic carbon distribution indicates that they are brought in by the minor river input. Enrichment of trace metals is clearly identified by the domination of Pb, Zn, Cd with high values than the average crustal values and comparison of trace metals from other coastal regions in the southeast coast of India. Statistical analysis clearly indicates that Fe and Mn control the distribution of trace metals and are concentrated in the finer particles and organic carbon fraction. The increase in concentration signifies the need for regular monitoring of the offshore coastal region in southeast coast of India which was recently destroyed by the 2004 December tsunami event, and which is also located near the Sethu Samuthram Ship Canal Project.     

Metal speciation and attenuation in stream waters and sediments contaminated by landfill leachate

The degree of metal contamination (Zn, Pb, Cu, Ni, Cd) has been investigated in the vicinity of an old unmonitored municipal landfill in Prague, Czech Republic, where the leachate is directly drained into a surface stream. The water chemistry was coupled with investigation of the stream sediment (aqua regia extract, sequential extraction, voltammetry of microparticles) and newly formed products (SEM/EDS, XRD). The MINTEQA2 speciation-solubility calculation showed that the metals (Zn, Pb, Cu, Ni) are mainly present as carbonate complexes in leachate-polluted surface waters. These waters were oversaturated with respect to Fe(III) oxyhydroxides, calcite (CaCO₃) and other carbonate phases. Three metal attenuation mechanisms were identified in leachate-polluted surface waters: (i) spontaneous precipitation of metal-bearing calcite exhibiting significant concentrations of trace elements (Fe, Mn, Mg, Sr, Ba, Pb, Zn, Ni); (ii) binding to Fe(III) oxyhydroxides (mainly goethite, FeOOH) (Pb, Zn, Cu, Ni); and (iii) preferential bonding to sediment organic matter (Cu). These processes act as the key scavenging mechanisms and significantly decrease the metal concentrations in leachate-polluted water within 200 m from the direct leachate outflow into the stream. Under the near-neutral conditions governing the sediment/water interface in the landfill environment, metals are strongly bound in the stream sediment and remain relatively immobile.     

Major and trace element geochemistry in Zeekoevlei, South Africa: A lacustrine record of present and past processes

This study reports a multi-parameter geochemical investigation in water and sediments of a shallow hyper-eutrophic urban freshwater coastal lake, Zeekoevlei, in South Africa. Zeekoevlei receives a greater fraction of dissolved major and trace elements from natural sources (e.g., chemical weathering and sea salt). Fertilizers, agricultural wastes, raw sewage effluents and road runoff in contrast, constitute the predominant anthropogenic sources, which supply As, Cd, Cu, Pb and Zn in this lake. The overall low dissolved metal load results from negligible industrial pollution, high pH and elevated metal uptake by phytoplankton. However, the surface sediments are highly polluted with Pb, Cd and Zn. Wind-induced sediment resuspension results in increased particulate and dissolved element concentrations in bottom waters. Low C/N ratio (10) indicates primarily an algal source for the sedimentary organic matter. Variation in sedimentary organic C content with depth indicates a change in primary productivity in response to historical events (e.g., seepage from wastewater treatment plant, dredging and urbanization). Primary productivity controls the enrichment of most of the metals in sediments, and elevated productivity with higher accumulation of planktonic debris (and siltation) results in increased element concentration in surface and deeper sediments. Aluminium, Fe and/or Mn oxy-hydroxides, clay minerals and calcareous sediments also play an important role in adsorbing metals in Zeekoevlei sediments.     

Particulate metal speciation in surficial sediments from Loch Dee, southwest Scotland, U.K.

The geochemical partitioning of ten elements in stratified Holocene sediments from Loch Dee, southwest Scotland, has been established by use of a five-stage sequential extraction procedure. Samples from below 15 cm sediment depth show minimal evidence of modification by anthropogenic contamination or active diagenesis and hold Fe, Mg, Cu, Cd, Co, Pb, and Ni primarily in detrital silicates or organic complexes, while Mn, Ca, and Zn reside largely in adsorbed and reducible oxide phases. In the uppermost ca 15 cm of sediment, enhanced total concentrations of Zn, Cu, and Pb reflect increased atmospheric deposition during the postindustrial period. Of these metals, only Pb displays any notable adjustment of partitioning in the enriched zone, showing disproportionate accumulation in labile oxides and organic-Pb phases. The lack of Pb and Zn carbonates in the contaminated horizon may reflect inherent thermodynamic instability under the acid surface and pore-water conditions of Loch Dee. Increments to total Mn and Co in the surficial ca 5 cm of sediment are attributable to the accumulation of secondary oxides and adsorbed species, consistent with precipitation from the interstitial pore-waters across a sedimentary redox front. The presence of metals such as Zn and Cd in soluble or acid-volatile phases in the interfacial sediment has implications for the future management of the Loch Dee basin, with leaching into the overlying waters likely, given the continuation of current trends of lake acidification.     

Mine drainage from the weathering of sulfide minerals and magnetite

Pyrite and pyrrhotite are the principal minerals that generate acid drainage in mine wastes. Low-pH conditions derived from Fe-sulfide oxidation result in the mobilization of contaminant metals (such as Zn, Cd, Ni and Cr) and metalloids (such as As) which are of environmental concern. This paper uses data from detailed mineralogical and geochemical studies conducted at two Canadian tailings impoundments to examine the mineralogical changes that pyrite, pyrrhotite, sphalerite and magnetite undergo during and after sulfide oxidation, and the subsequent release and attenuation of associated trace elements. The stability of sphalerite in tailings impoundments generally is greater than that of pyrrhotite, but less than pyrite. Dissolved Ni and Co derived from Fe sulfides, and to a lesser extent, dissolved Zn and Cd from sphalerite, are commonly attenuated by early-formed Fe oxyhydroxides. As oxidation progresses, a recycling occurs due to continued leaching from low-pH pore waters and because the crystallinity of Fe oxyhydroxides gradually increases which decreases their sorptive capacity. Unlike many other elements, such as Cu, Pb and Cr, which form secondary minerals or remain incorporated into mature Fe oxyhydroxides, Zn and Ni become mobile. Magnetite, which is a potential source of Cr, is relatively stable except under extremely low-pH conditions. A conceptual model for the sequence of events that typically occurs in an oxidizing tailings impoundment is developed outlining the progressive oxidation of a unit of mine waste containing a mixed assemblage of pyrrhotite and pyrite.     

The natural attenuation of two acidic effluents in Tharsis and La Zarza-Perrunal mines (Iberian Pyrite Belt, Huelva, Spain)

The geochemical evolution of two acid mine effluents in Tharsis and La Zarza-Perrunal mines (Iberian Pyrite Belt, Huelva, Spain) has been investigated. In origin, these waters present a low pH (2.2 and 3.1) and high concentrations of dissolved sulphate and metals (Fe, Al, Mn, Cu, Zn, As, Cd, Co, Cr, Ni). However, the natural evolution of these acidic waters (which includes the bacterial oxidation of Fe(II) and the subsequent precipitation of Fe(III) minerals) represents an efficient mechanism of attenuation. This self-mitigating process is evidenced by the formation of schwertmannite, which retains most of the iron load and, by sorption, toxic trace elements like As. The later mixing with pristine waters rises the pH and favours the total precipitation of Fe(III) at pH 3.5 and, subsequently, Al compounds at pH 4.5, along with the sorption of trace metals (Mn, Zn, Cu, Cd, Co, Ni) until chemical equilibrium at circumneutral conditions is achieved.     

The role of sulphide and carbonate minerals in the concentration of chalcophile elements in the bituminous coal seams of a paralic series (Upper Carboniferous) in the Upper Silesian Coal Basin (USCB), Poland

Sulphide and carbonate minerals from nine bituminous coal seams of a Paralic Series were investigated by means of polished-section microscopy, scanning electron microscopy and absorption spectral analyses. In addition to syngenetic accumulations of kaolinite, illite and quartz, diagenetic veinlets of subhedral pyrite and marcasite most often occur in vitrinite clast fissures and in post-tectonic fissures, nests and lenses with fusinite. Epigenetic anhedral and subhedral grains of ankerite, dolomite, siderite and calcite are also frequently found in post-tectonic veins. Pyrite replaced some of the marcasite grains and it dominates in older coal seams in the Flora Beds as compared with the Grodziec Beds. Occasionally there are anhedral and subhedral galena, sphalerite and chalcopyrite grains among coal macerals as well as cerussite among post-tectonic carbonate veins. They all represent the only minerals that are abundant in definite chalcophile elements (Cd, Co, Cu, Ni, Pb, Zn). In addition to the minerals just mentioned, the elements occurred in pyrite and ankerite grains, which contained inclusions of fusinite and other minerals (among others, clay and carbonate minerals in pyrite, pyrite in carbonates). Although there is a low content of minerals accumulating Cd, Co, Cu, Ni, Pb and Zn, the minerals significantly influence the average concentration of elements in the coal seams. In the Grodziec Beds, mineral matter, especially carbonates and sulphides, determines (>50%) the concentration of Cd, Cu, Pb and Zn in coal. The basic part of Cd, Co and Ni in the coal seams of the Grodziec Beds and of Co, Cu, Ni, Pb and Zn in coal seams of the Flora Beds originates from organic matter. These regularities can be important, from an ecological perspective, in stating whether the coals investigated are useful for combustion and in chemical processing.     

Experimental modeling of the immobilization of heavy metals at the carbonate adsorption–precipitation geochemical barrier

Experimental data obtained on the adsorption–precipitation immobilization of heavy metals (Cu, Zn, Pb, Cd, Co, and Ni) from acidic and neutral solutions by calcite and dolomite demonstrate that interaction of solutions of heavy metals with these minerals at pH > 7.8–8.1 leads to a significant decrease in the concentrations of the metals because of the crystallization of carbonates of these metals. Except Pb, which is equally removed from solutions by both minerals, the immobilization efficiency of the metals on dolomite is greater than on calculate at the same pH. Residual Zn, Cd, Co, and Ni concentrations are immobilized by chemosorption, which is the most efficient for Cd and less significant for Co, Ni, and Zn. It is proved that artificial geochemical barriers on the basis of carbonate rocks can be efficiently applied to protect environment from contamination with heavy metals.     

Thermodynamic modeling of heavy metal forms in bottom sediments: By the example of the Ivankovsky Reservoir

The technique of thermodynamic modeling for interactions in system “pore water-solid phase of bottom sediments” is suggested (including dissolved and sorbed forms of heavy metals). The main sorbent phases (clay minerals, iron and manganese hydroxides, and organic matter) are presented as multi-component ideal solid solutions. The capacities of sorbing phases are calculated according to the results of selective extraction by the Tessier scheme supplemented with determination macro-cations. The selectivity constants and free energy of metal bonding (Fe, Mn, Zn, Cu, Ni, Pb, Co, and Cd) with sorbing phases are calculated for bottom sediments of various compositions within the Ivankovsky Reservoir and the estimation of their natural variations is given.     

Geochemical variations of major and trace elements in recent sediments,off the Gulf of Mannar,the southeast coast of India

The Gulf of Mannar along the Tuticorin coast is a coral base of the southeast coast of India. To obtain a preliminary view of its environmental conditions, geochemical distribution of major elements (Si, Al, Fe, Ca, Mg, Na, K, P), trace elements (Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) and acid leachable elements (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) were analyzed in surface sediment samples from two seasons. Geochemical fractionation confirmed the lithogenic origin of metals, which were mainly associated with the detrital phase. The sediments in the gulf are sandy with abundant calcareous debris, which controls the distribution of total and acid leachable elements. Enrichment factors relative to crust vary by a magnitude of two to three and the presence of trace metals indicates the input of Cr, Pb, Cd, Cu and Zn in both forms through industrial activities. Factor analysis supports the above observation with higher loadings on acid leachable elements and its association with CaCO₃. The increase in concentration of trace metals (Cr, Pb, Cd, Cu, Co, Ni, Zn) along the Gulf of Mannar indicates that the area has been contaminated by the input from riverine sources and the industries nearby. The present study indicates that other sources should be evaluated in the long-term monitoring program.     

Geochemistry of trace metals associated with reduced sulfur in freshwater sediments

Porewater concentration profiles were determined for Fe, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn), sulfide, SO₄ and pH in two Canadian Shield lakes (Chevreuil and Clearwater). Profiles of pyrite, sedimentary trace elements associated with pyrite and AVS were also obtained at the same sites. Thermodynamic calculations are used, for the anoxic porewaters where sulfide was measured, to characterize diagenetic processes involving sulfide and trace elements and to illustrate the importance of sulfide, and possibly polysulfides and thiols, in binding trace elements. The ion activity products (IAP) of Fe sulfide agree with the solubility products (K_s) of greigite or mackinawite. For Co, Ni and Zn, IAP values are close to the K_S values of their sulfide precipitates; for Cu and Pb, IAP/K_s indicate large oversaturations, which can be explained by the presence of other ligands (not measured) such as polysulfides (Cu) and thiols (Pb). Cobalt, Cu, Ni and Zn porewater profiles generally display a decrease in concentration with increasing ΣH₂S, as expected for transition metals, whereas Cd, Pb and Zn show an increase (mobilisation). The results suggest that removal of trace elements from anoxic porewaters occurs by coprecipitation (As and Mn) with FeS(s) and/or adsorption (As and Mn) on FeS(s), and by formation of discrete solid sulfides (Cd, Cu, Ni, Pb, Zn and Co). Reactive Fe is extensively sulfidized (51–65%) in both lakes, mostly as pyrite, but also as AVS. Similarities between As, Co, Cu and Ni to Fe ratios in pyrite and their corresponding mean diffusive flux ratios suggest that pyrite is an important sink at depth for these trace elements. High molar ratios of trace elements to Fe in pyrite from Clearwater Lake correspond chronologically to the onset of smelting activities. AVS can be an important reservoir of reactive As, Cd and Ni and, to a lesser extent, of Co, Cu and Pb. Overall, the trace elements most extensively sulfidized were Ni, Cd and As (maximum of 100%, 81% and 49% of the reactive fraction, respectively), whereas Co, Cu, Mn, Pb and Zn were only moderately sulfidized (11–16%).     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.     

Speciation and Mobility of Selected Trace Metals (As, Cu, Mn, Pb and Zn) in Sediment with Depth in Cam River-Mouth, Haiphong, Vietnam

The speciation and mobility of some selected trace metals (As, Cu, Mn, Pb and Zn) in sediments with depth was investigated in the Cam River-mouth (Vietnam) by collecting sediment cores and analysing porewater and sediment composition, complemented with single (ammonium-EDTA) and sequential (BCR 3-step) extractions and mineralogical analysis (XRD). All trace metals show overall decreasing trends with depth in porewater as a result of anthropogenic input in upper sediment layers. High porewater concentrations of As, Mn and Pb in oxic and suboxic sediment layers may result in groundwater pollution. Sediment-bound Pb and Mn dominate in the reducible and the acid-soluble fraction, respectively, while Cu and Zn distribute rather evenly between four extracted fractions. The porewater metal speciation, as predicted by a geochemical model Visual MINTEQ version 3.0, indicates that the toxicity of Cu, Mn, Pb and Zn (presented by the proportions of free metal ions) decreases with depth, while the toxicity of As increases when As(III) becomes more abundant. The dissolved concentrations of trace metals are not only controlled by the precipitation/dissolution of discrete hydroxide/oxide, carbonate and phosphate minerals, but also by sorption processes on major sorbents (i.e. As on goethite, and Mn and Zn on calcite and dolomite). Sulphide minerals do not show any control even in the anoxic zone most likely because of the low concentration of sulphur.     

Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

The Heavy Metals Speciations in Bottom Sediments of Vyshny Volochek Reservoir

The water ecosystem of the Vyshny Volochek Reservoir is characterized based on the study of the distribution of heavy metals speciations in the solid phase and pore waters of bottom sediments. Using the sequential extraction procedure, it is shown that Mn is mainly present in exchangeable and carbonate-bound forms; significant roles for Fe, Zn, Pb, and Co are played by forms that are bound to iron and manganese hydroxides and Cu and Ni are mainly bound to organic matter. Thermodynamic calculations have established the prevailing share of the following forms in pore waters: free ions for Zn, Ni, Co, and Cd, carbonate complexes for Pb, and fulvic complexes for Cu. It has been revealed that the speciation forms of heavy metals in bottom sediments depend on the lithological features and content of organic matter in sediments.     

Mobility of major-, minor- and trace elements in solutions of a planosolic soil: Distribution and controlling factors

Subsurface waters circulating in an unpolluted soil of a planosolic horizon (Massif Central, France) were studied in order to determine their physico-chemical characteristics. Three water sampling sites were chosen along a toposequence. For each site, two piezometers were placed above and in the gravelly and concretion-rich horizon (Fe- and Mn- oxyhydroxides). Concentrations of major-, minor- (cations, anions, Fe, Mn, P and Si) and trace elements (Al, Ba, Cd, Co, Cr, Cu, Ni, Pb, Rb, Sr, Zn and U) were monitored on bulk and filtered water (0.45 μm) to study both the particulate and the dissolved components, from 2004 to 2006, during the soil saturation period (i.e., from November to May). Chemical characteristics of soil solutions provide evidence for various chemical water compositions and for temporal variations of water quality, revealing that the hydrodynamic and chemical reactivity in the solution is different for the three sites. Calculations of pe values indicate a range of redox state of the soil solutions. The pe ranges are different for each piezometer but correspond to anoxic solution. For all piezometers, distribution between the dissolved and the particulate fraction and correlations between the various elements in the soil solutions indicate that: (i) Al and Fe show similar behaviour, (ii) Al is mainly present as oxyhydroxides and (iii) some trace metals are mainly associated with particles which have a mixed nature. The impact of a concretion-rich horizon is noticed both on the nature of particles and on the speciation of trace metals and could be explained by the hydrodynamic and chemical reactivity of the circulating solution. Very few correlations exist between elements in the dissolved phase.     

Trace metal speciation in sea and pore water of the Gotland Deep,Baltic Sea, 1994

Studies on the speciation (particulate, colloidal, anionic and cationic forms) of trace metals (Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Zn) in the water column and in pore waters of the Gotland Deep following the 1993/94 salt-water inflows showed dramatic changes in the total “dissolved” metal concentrations and in the ratios between different metal species in the freshly re-oxygenated waters below 125 m. Changes in concentrations were greatest for those metals for which the solubility differs with the redox state (Fe, Mn, Co) but were also noted for those metals which form insoluble sulphides (Cd, Pb, Cu, Zn) and/or stable complexes with natural ligands (Cu). Pore water data from segmented surface muds (0–200 mm) indicated that significant redox and related metal speciation changes took place in the surface sediments only a few weeks after the inflow of the oxygenated sea water into the Gotland Deep.