The influence of hydrous Mn–Zn oxides on diel cycling of Zn in an alkaline stream draining abandoned mine lands

Many mining-impacted streams in western Montana with pH near or above neutrality display large (up to 500%) diel cycles in dissolved Zn concentrations. The streams in question typically contain boulders coated with a thin biofilm, as well as black mineral crusts composed of hydrous Mn–Zn oxides. Laboratory mesocosm experiments simulating diel behavior in High Ore Creek (one of the Montana streams with particularly high Zn concentrations) show that the Zn cycles are not caused by 24-h changes in streamflow or hyporheic exchange, but rather to reversible in-stream processes that are driven by the solar cycle and its attendant influence on pH and water temperature (T). Laboratory experiments using natural Mn–Zn precipitates from the creek show that the mobilities of Zn and Mn increase nearly an order of magnitude for each unit decrease in pH, and decrease 2.4-fold for an increase in T from 5 to 20 °C. The response of dissolved metal concentration to small changes in either pH or T was rapid and reversible, and dissolved Zn concentrations were roughly an order of magnitude higher than Mn. These observations are best explained by sorption of Zn²⁺ and Mn²⁺ onto the secondary Mn–Zn oxide surfaces. From the T-dependence of residual metal concentrations in solution, approximate adsorption enthalpies of +50 kJ/mol (Zn) and +46 kJ/mol (Mn) were obtained, which are within the range of enthalpy values reported in the literature for sorption of divalent metal cations onto hydrous metal oxides. Using the derived pH- and T-dependencies from the experiments, good agreement is shown between predicted and observed diel Zn cycles for several historical data sets collected from High Ore Creek.     

Diel variation of arsenic,molybdenum and antimony in a stream draining natural As geochemical anomaly

The Mokrsko Stream in the central Czech Republic is an oxic and slightly alkaline stream that drains a natural As geochemical anomaly. Although long-term monitoring has characterized the general seasonal trends in trace element concentrations (i.e., As, Mo, Cu, Zn) in this stream, little is known about solubility controls and sorption processes that influence diel cycles in trace element concentrations. Trace elements (including As species, Cu, Mn, Mo, Pb and Sb) and other parameters were monitored over two 24-h periods in unfiltered and filtered (0.1 μm) samples collected in August 2010 and June 2011. Copper and Pb were predominantly (>92% of the mass) associated with the particulate fraction (>0.1 μm). Arsenic, Mo and Sb were predominantly (>88% of the mass) in the “dissolved” (<0.1 μm) form. Particulate-associated elements displayed up to a factor of 13 differences between minimum and maximum concentrations, most likely due to increased streamflow related to rainfall events. Dissolved concentrations of the trace metal cations (Cu, Fe, Mn and Pb) were consistently low and displayed no diel trends. Dissolved As(V), Mo and Sb varied on a diel cycle, with increased concentrations (up to 36%) during the late afternoon and decreased concentrations during the nighttime. Diel trends in trace anionic elements are explained by temperature-dependent sorption, as the diel changes in pH during base flow were very small (0.07 std. units). Very low concentrations of As(III), which have been shown to vary in a diel cycle, were attributed to enhanced hydraulic exchange with As(III)-rich hyporheic water during rainfall events.     

Short-term changes in water chemistry in the Baccu Locci stream (Sardinia,Italy) affected by past mining

Short-term changes in water chemistry, and especially in dissolved trace element concentrations, associated with diel cycles during base-flow conditions at a specific sampling station in the Baccu Locci stream draining the homonymous old mine area in Sardinia (Italy) were investigated. Diel fluctuations in pH and alkalinity were correlated with the temperature-dependent CO₂ solubility and the biologically-induced CO₂ production, both of which were higher during the night. Adsorption/desorption to/from streambed material, in particular ferrihydrite, is believed to be the main in-stream mechanism causing the observed diel variations in dissolved concentrations of As and Zn. Arsenic was mainly affected by the dual action of temperature and competing carbonate ions, whereas pH seemed less important. Temperature acted in accordance with the exothermic feature of anion sorption onto hydrous metal oxide surfaces; aqueous carbonate species exerted their competitive effect in relation to alkalinity variation. Zinc was primarily affected by temperature, in accordance with the endothermic feature of metal cation sorption onto hydrous metal oxide surfaces, and secondly by pH. Co-precipitation of As and Zn with calcite is another possible mechanism, which requires further investigation involving examination of inorganic and biological materials coating the streambed. All these processes potentially controlling the diel cycles of trace elements should be carefully considered to assess the effectiveness of remediation actions currently in progress at Baccu Locci. A normalization method for data from asynchronous sampling has been developed and proposed in order to eliminate or at least attenuate the effect of sampling time and provide an additional tool to identify the processes/mechanisms involved in trace element concentration fluctuations observed along a contaminated stream during base-flow conditions.     

Diurnal variations in,and influences on,concentrations of particulate and dissolved arsenic and metals in the mildly alkaline Wallkill River,New Jersey,USA

Diurnal variations in particulate and dissolved As and metal concentrations were observed in mildly alkaline water from a wetlands site on the Wallkill River in northwestern New Jersey. The site, underlain by glacial sediments over dolomite bedrock, is 10 km downstream from a mined area of the Franklin Marble, host to Zn ores, also As and Mn minerals. In mid-September 2005, maxima and minima in dissolved-oxygen-concentration and pH, typically caused by photosynthesis and respiration, occurred at 2000 and 0800 hours. Concentrations of dissolved As (1.52–1.95 μg/L) peaked at dusk (2000 hours), whereas dissolved Mn and Zn concentrations (76.5–96.9 and 8.55–12.8 μg/L, respectively) were lowest at dusk and peaked at 1000 hours. These opposing cycles probably reflect sorption and desorption of As (an anion), and Mn and Zn (cations) as pH varied throughout the 24-h period. Doubly-peaked cycles of B, Cl, SO₄, and nutrients also were observed; these may result from upstream discharges of septic-system effluent. Both recoverable amd particulate Al, Fe, Mn, and Zn concentrations peaked between 0200 and 0600 hours. The particulate metals cycle, with perturbations at 0400 hours, may be influenced by biological activity.     

Assessment of diel chemical and isotopic techniques to investigate biogeochemical cycles in the upper Klamath River,Oregon, USA

The upper Klamath River experiences a cyanobacterial algal bloom and poor water quality during the summer. Diel chemical and isotopic techniques have been employed in order to investigate the rates of biogeochemical processes.Four diel measurements of field parameters (temperature, pH, dissolved oxygen concentrations, and alkalinity) and stable isotope compositions (dissolved oxygen–δ¹⁸O and dissolved inorganic carbon–δ¹³C) have been performed between June 2007 and August 2008. Significant diel variations of pH, dissolved oxygen (DO) concentration, and DO–δ¹⁸O were observed, due to varying rates of primary productivity vs. respiration vs. gas exchange with air. Diel cycles are generally similar to those previously observed in river systems, although there are also differences compared to previous studies. In large part, these different diel signatures are the result of the low turbulence of the upper Klamath River. Observed changes in the diel signatures vs. sampling date reflect the evolution of the status of the algal bloom over the course of the summer.Results indicate the potential utility of applying diel chemical and stable isotope techniques to investigate the rates of biogeochemical cycles in slow-moving rivers, lakes, and reservoirs, but also illustrate the increased complexity of stable isotope dynamics in these low-turbulence systems compared to well-mixed aquatic systems.     

Diel variation of selenium and arsenic in a wetland of the Great Salt Lake, Utah

Diel (24-h) changes in Se and As concentrations in a freshwater wetland pond bordering the Great Salt Lake (GSL) were examined. Selenium concentrations (filtered and unfiltered) changed on a diel basis, i.e., were depleted during early morning and enriched during daytime over August 17-18. During the May 24-25, 2006 and September 29-30 diel studies, no significant 24-h trends were observed in Se concentrations compared to August, which showed daily maximums up to 59% greater than the daily minimum. Both filtered and unfiltered As concentrations also varied on a diel cycle, with increased concentrations during early morning and decreased concentrations during daytime. Filtered As concentrations increased 110% during the May 24-25, 2006 diel study. Selenium varied in phase with pH, dissolved O₂ (DO), and water temperature (T_w) whereas As varied opposite to Se, pH, DO and T_w. Changes in pH, DO and T_w showed a direct linear correlation (r = 0.74, 0.75, and 0.55, respectively) to filtered Se. Also pH, DO and T_w were inversely correlated to filtered As concentration (r = −0.88, −0.87, and −0.84, respectively). Equilibrium geochemical speciation and sorption models were used to examine the potential oxidation state changes in Se and As, and sorption and desorption reactions corresponding to the observed 24-h variations in pe and pH. In this wetland it was postulated that diel Se variation was driven by sorption and desorption due to photosynthesis-induced changes in pH and redox conditions. Diel variations of As were hypothesized to be linked to pH-driven sorption and desorption as well as co-precipitation and co-dissolution with mineral phases of Mn.     

Size Fractionation (Dissolved, Colloidal and Particulate) of Trace Metals in the Thur River, Switzerland

The distribution of some trace metals (Cu, Zn, Ni, Co,Fe, Mn) and of DOC over a particulate (> 1 m),a colloidal (size < 0.45 m and molecular weight > 10 kD) and an ultrafiltered fraction (< 10 kD)was determined at several sites on the Thur River,Switzerland, at various times of the year. Thecomplexation of Cu by strong ligands in theultrafiltrate and in the conventional filtrate (<0.45 m) was compared using a ligand-exchange/CSV method.The <0.45 m concentrations of Cu (from anaverage of 7 nM to 24 nM), Zn (<5–23 nM), Ni (5–13 nM),Co (1.5–3 nM) and Mn (7–92 nM)increased downstream. The major part of Cu, Zn, Niand Co usually occurred in the ultrafiltratefraction at all sites, whereas Fe and Mn were mostlyin the particulate fraction, under conditions of lowsuspended matter content (< 10 mg L^-1) in theriver. The percentage of metal in the colloidalfraction, with respect to the 0.45-m filtrate,decreased in the order: Cu (median 11%) > Zn Ni(median 5–6%) > Mn Co (median < 5%). DOCalso consisted mostly of molecules in the < 10 kDrange.Cu was strongly complexed by natural organic ligandsin all filtrate and ultrafiltrate samples. A largepart of the strong Cu binding ligands consisted ofcompounds in the < 10 kD range, but colloidalligands with similar properties also occurred. Cu wasdistributed among the dissolved and the colloidalligands, roughly in proportion to organic carbon.The colloidal fraction (as defined here) did notincrease in its proportional amount downstream and wasonly of limited significance in transporting traceelements in the Thur River under low discharge conditions.     

Isotopic variations of dissolved copper and zinc in stream waters affected by historical mining

Zinc and Cu play important roles in the biogeochemistry of natural systems, and it is likely that these interactions result in mass-dependent fractionations of their stable isotopes. In this study, we examine the relative abundances of dissolved Zn and Cu isotopes in a variety of stream waters draining six historical mining districts located in the United States and Europe. Our goals were to (1) determine whether streams from different geologic settings have unique or similar Zn and Cu isotopic signatures and (2) to determine whether Zn and Cu isotopic signatures change in response to changes in dissolved metal concentrations over well-defined diel (24-h) cycles.Average δ⁶⁶Zn and δ⁶⁵Cu values for streams varied from +0.02‰ to +0.46‰ and −0.7‰ to +1.4‰, respectively, demonstrating that Zn and Cu isotopes are heterogeneous among the measured streams. Zinc or Cu isotopic changes were not detected within the resolution of our measurements over diel cycles for most streams. However, diel changes in Zn isotopes were recorded in one stream where the fluctuations of dissolved Zn were the largest. We calculate an apparent separation factor of ∼0.3‰ (^66/64Zn) between the dissolved and solid Zn reservoirs in this stream with the solid taking up the lighter Zn isotope. The preference of the lighter isotope in the solid reservoir may reflect metabolic uptake of Zn by microorganisms. Additional field investigations must evaluate the contributions of soils, rocks, minerals, and anthropogenic components to Cu and Zn isotopic fluxes in natural waters. Moreover, rigorous experimental work is necessary to quantify fractionation factors for the biogeochemical reactions that are likely to impact Cu and Zn isotopes in hydrologic systems. This initial investigation of Cu and Zn isotopes in stream waters suggests that these isotopes may be powerful tools for probing biogeochemical processes in surface waters on a variety of temporal and spatial scales.     

Heavy metal contamination in overbank sediments of the Geul river (East Belgium): Its relation to former Pb-Zn mining activities

Overbank sediments of the Geul River (East Belgium) are highly contaminated by the heavy metals Pb, Zn, and Cd due to former Pb-Zn mining activities in the drainage basin. Geochemical variations in vertical overbank sediment profiles sampled 1 km north of the mine tailings of Plombiéres allow metal fluxes back to the 17th century to be reconstructed. The vertical profiles are subdivided into three major units corresponding to different industrial periods based on sedimentological criteria as well as on the distribution of contaminants. Alluvial sediments with the highest heavy metal concentrations correspond to the major period of mining activity of the 19th century. The fact that Zn mining at the La Calamine open mine started before large-scale mining of the PbS-ZnS subsurface exploitations is reflected in the vertical profiles by an increase in Zn content before a marked increase in Pb and Cu. The regional extent of contamination in the alluvial deposits was evaluated on the basis of the geochemical analysis of sediments at depths of the 0–20 cm and 80–100 cm. Most of the upper samples are extremely contaminated. Significant local variations in heavy metal concentration in the lower samples are interpreted in terms of which overbank sediment horizon has been sampled at a depth of 80–100 cm. This indicates that blind sampling of overbank sediments to characterize the degree of contamination in shallow boreholes can give very erratic results.     

High-resolution profiles of trace metals assessed by DGT techniques in lake sediment porewaters

The technique of diffusive gradients in thin films (DGT) was applied to obtain high-resolution vertical profiles of trace metals in sediment porewater of a eutrophic lake, Lake Chaohu. All sampling sediments were under anaerobic conditions with Eh values below 0, the redox potential profile in M4 was relatively stable, and higher Eh values in M4 than that in M1 were observed due to hydrodynamic effects. Fe, Mn and As exhibited closely corresponding profiles due to the co-release of Fe and Mn oxides and the reduction of As. Higher Fe and Mn concentrations and lower As concentrations were observed in M1 of the western half-lake than those in M4 of the eastern half-lake due to different sources and metal contamination levels in the two regions. Cu and Zn showed increasing concentrations similar to Mn and Fe at 1–2 cm depth of sediments, while DGT measured Co, Ni, Cd and Pb concentrations decreased down to 3–4 cm in the profiles. Co, Ni, Cu, Zn, Cd and Pb showed insignificant regional concentration variances in the western and eastern half-lakes. According to the R(C _DGT/C _{centrifugation}) values, the rank order of metal labilities decrease as follows: Fe (>1) > Cu, Pb, Zn (>0.9) > Co, Ni, Cd (>0.3) > Mn, As (>0.1).     

Seasonal variations of Zn, Cu, As and Mo in arsenic-rich stream at the Mokrsko gold deposit, Czech Republic

Monthly sampling of slightly alkaline arsenic-rich stream in the Mokrsko gold deposit revealed seasonal variations in dissolved Zn, Cu, As and Mo. Concentrations of trace metal cations (Zn, Cu) increased as much as 330 and 178%, respectively, from minimum mean values at autumn to maximum mean values at spring. In contrast, concentrations of trace element oxyanions (As, Mo) revealed opposite seasonal pattern with increase to 189% (As) and 123% (Mo) during summer–autumn, indicating that in-stream biogeochemical process(es) played the main role in controlling the seasonal variations of these trace elements. The trace elements were mainly scavenged by low crystalline Mn oxyhydroxide and Fe oxyhydroxide (ferrihydrite). Results are consistent with sorption and coprecipitation processes controlling seasonal variations of dissolved Zn and Cu, while As and Mo dynamics appear linked to Mn redox reactions. The sorption processes and Mn redox processes are attributed to the changes of pH and oxic/anoxic conditions on the surface of oxyhydroxides, respectively, which are themselves controlled by the balance between photosynthesis and respiration. Under the geochemical conditions of the stream, inferred Mn redox reactions can only be explained by microbial activity.     

Heavy metal contamination in the Arieş river catchment, western Romania: Implications for development of the Roşia Montană gold deposit

The Abrud–Arieş river system, western Romania, is subject to ongoing mining activity associated with Cu, Pb and Zn ore extraction. The catchment contains what is believed to be Europe's largest unutilized Au deposit at Roşia Montană that is planned to be exploited by open-cast mining techniques. The magnitude and environmental significance of metal (Cd, Cu, Pb, and Zn) concentrations in surface water and river channel sediment have been investigated along a 140 km reach of the Rivers Abrud and Arieş and 9 tributaries affected by mining. The speciation of sediment-bound metals was established using a 4-stage sequential extraction procedure (SEP) that identified four chemical phases: (1) exchangeable, (2) Fe/Mn oxides, (3) organic matter/sulphides and (4) residual. Peak solute and sediment-bound metal concentrations were found to occur in the River Abrud downstream of the EM Bucium mine and in mining-affected tributaries, with up to 71% of sites containing sediment metal concentrations in excess of Dutch intervention values. The River Arieş was found to be much less polluted than the River Abrud, with only Cu showing concentrations above guideline values, as a consequence of porphyry Cu mineralization in the catchment. The magnitude and spatial extent of metal pollution is influenced by local physico-chemical conditions and hydrological linkages between mining and local river systems. Sediment-bound Cd and Zn were found to be predominantly associated with the exchangeable phase of the sediment (9–74% and 6–65%, respectively), whilst Fe/Mn oxides (5–76%) and organic matter/sulphides (1–45%) generally accounted for a majority of Pb and Cu partitioning, respectively. Sites of environmentally significant sediment-metal pollution were identified in the Rivers Abrud and Arieş where exchangeable metal concentrations exceeded Dutch intervention values. The implications of metal contamination in the Arieş river basin to the proposed mining development at Roşia Montana are discussed in relation to other contaminated Romanian catchments and with the EU Water Framework Directive.     

Physico-chemical seasonal variability of a tropical estuary: major and minor elements in water and air

The lower reaches of the Coatzacoalcos River in southeast Mexico is an area of intense industrial development. The physico-chemical characteristics of the area have exhibited differences over the years. Apparently from the associated outcroppings of limestone in the Uxpanapa River Basin, the major elements that are dissolved show higher concentrations of Ca, Mg and HCO₃^– in the waters supplied by this river. The water in the Calzadas River contains high concentrations of Ca, SO₄ and HCO₃^– that are associated with the saline domes crossed by this river. Due to industrial discharges, the sulfate concentration is very high in the water and air during April. Nitrate concentration diminishes with salinity. Higher nitrate as well as nitrite and ammonia levels are present during flood season. Phosphate concentration, associated with high oxygen levels, is higher in January. Zn, Cu and Cr are higher during the dry season (April) when dilution is minimal and low levels of TOC are present. The smaller concentrations of Zn and Cu observed in January are associated with high TOC values in water. The lower levels of Cr present in August are associated with high amounts of suspended matter. Pajaritos Lagoon and Teapa-L, with large industrial discharges, have the highest nutrient and dissolved metal concentrations in the area. Air particles smaller than 2.5 m contain Fe, V, Ti, Cu, Zn, and high amounts of S. These anomalous concentrations of sulfates and metals are attributed to anthropogenic sources.     

Effectiveness of sulfate-reducing passive bioreactors for treating highly contaminated acid mine drainage: II. Metal removal mechanisms and potential mobility

Column bioreactors were used for studying mechanisms of metal removal, assessment of long-term stability of spent reactive mixtures, as well as potential metal mobility after treating highly contaminated acid mine drainage (AMD; pH 2.9–5.7). Several physicochemical, microbiological, and mineralogical analyses were performed on spent reactive mixtures collected from 4 bioreactors, which were tested in duplicate for two hydraulic retention times (7.3d and 10d), with downward flow over an 11-month period. Consistent with the high metal concentrations in the AMD feed, and with low metal concentrations measured in the treated effluent, the physicochemical analyses indicated very high concentrations of metals (Fe, Mn, Cd, Ni, and Zn) in the top and bottom layers of the reactive mixtures from all columns. Moreover, the concentrations of Fe (50.8–57.8 g/kg) and Mn (0.53–0.70 g/kg) were up to twice as high in the bottom layers, whereas the concentrations of Cd (6.77–13.3 g/kg), Ni (1.80–5.19 g/kg) and Zn (2.53–13.2 g/kg) were up to 50-times higher in the top layers. Chemical extractions and elemental analysis gave consistent results, which indicated a low fraction of metals removed as sulfides (up to 15% of total metals recovered in spent reactive mixtures). Moreover, Fe and Mn were found in a more stable chemical form (residual fraction was 42–74% for Mn and 30–77% for Fe) relative to Cd, Ni or Zn, which seemed more weakly bound (oxidisable/reducible fractions) and showed higher potential mobility. Besides identifying (oxy)hydroxide and carbonate minerals, the mineralogical analyses identified metal sulfides containing Fe, Cd, Ni and Zn. Metal removal mechanisms were, therefore, mainly adsorption and other binding mechanisms with organic matter (for Cd, Ni and Zn), and the precipitation as (oxy)hydroxide minerals (for Fe and Mn). After 15 months, however, the column bioreactors did not lose their capacity for removing metals from the AMD. Although the metals were immobile during the bioreactor treatment, their mobility could increase from spent reactive mixtures, if stored inappropriately. Metal recovery by acidic leaching of spent substrates at the end of bioreactor operation could be an alternative.     

Influence of Temporal Variations in River Discharge, pH, Alkalinity and Ca on the Speciation and Concentration of Heavy Metals in Some Mining Polluted Rivers

Dissolved (dialysis in situ) and total concentrations ofCu, Zn, Cd and Al in eight mining polluted rivers in the Røros area, central Norway, were determinedby atomic absorption spectrometry (flame and graphite furnace) and compared to pH, Caconcentration and alkalinity through seasonal variations in river discharge. Totalconcentrations of the metals were highest during early spring flood and during summer andautumn rain episodes. Dissolved concentrations also increased as the spring floodproceeded, but small discharge peaks within this 2 month period as well as a considerableautumn flood episode appeared to lower rather than to raise the dissolved metal concentrations.Consequently the dissolved fractions of Zn, Cd and Al showed a significant negative correlationwith river discharge, and were low at the discharge peaks. Possibly high sediment concentrationsoccurring at high flood conditions more than counteracted desorption induced by pHdecrease, and led to decreased dissolved fractions through adsorption. Cu speciationon the other hand seemed to be more closely linked to pH. Alkalinity and Ca concentration,both assumed to protect aquatic life from metal pollution, were significantly lowerduring episodes with high Cu and Al total concentrations.     

Granulometric and chemical composition of the Sava River sediments upstream and downstream of the Krsko nuclear power plant

Total concentrations of 13 elements (K, Ca, Ti, Cr, Mn, Fe, Cu, Zn, Rb, Sr, Y, Zr, Pb) in the size-fractionated Sava River sediments upstream and downstream of the Krsko nuclear power plant together with metal speciation within bulk sediment have been investigated. Trace metals generally increase with decreasing particle size, however, because of entrapment of organic matter in the 0.63–1 mm fraction, concentrations in the coarser sediment fraction are higher than expected. Exchangeable Pb, Zn, Cu, Mn, Cr and Fe are generally found to represent a negligible fraction of the total metal concentration of the bulk sediment. Seasonal variations of the Pb, Zn and Cu concentrations in the <0.5 mm fraction reflect decreased values during the spring period. Heavy metal concentrations in the 2003 waste water discharges from the Krsko nuclear power plant released into the Sava River were much lower than their maximum allowed values. Combined rubidium and organic matter normalization of the Zn, Pb and Cu concentrations, which was applied on the minus 0.063 mm fraction, indicated three potential sources of contaminants.     

Trace metals in suspended particulate matter and in sediment trap material from a permanently anoxic fjord — Framvaren, South Norway

Geochemical studies of the trace metal concentrations in suspended particulate matter (SPM) and sediment trap material from a permanently anoxic fjord, Framvaren, South Norway in 1989 and 1993 indicate that extremely high concentrations of zinc (max = 183920 mg/kg), copper (max = 4130 mg/kg), lead (max = 2752 mg/kg), and cadmium (max= 8.1 mg/kg) sometimes (1993) occur in the SPM collected in the anoxic water layer. The highest concentrations of Zn occur just below the redoxcline at 22 m water depth (in 1993), and copper, lead and cadmium have maximum concentrations between 30 and 80 m depth, where the amount of total SPM is at a minimum (about 0.3 mg/L). On a mass per volume (g/L) basis, the maximum concentrations of Cd, Cu and Fe occur at the interface (21m) and those of Zn occur just below the redoxcline (22 m depth). The SPM and sediment trap data suggest that the metals are precipitated as sulfide minerals in the anoxic water. The presence of particulate sulfides was confirmed by SEM studies that show the occurrence of discrete metal (Cu, Fe, Pb, and Zn) sulfide particles in size from 10–20 m as well as framboidal pyrites (1–5 m in size). Higher levels of metal sulfides at intermediate depths rather than in the deep water of Framvaren (> 100 m), may be due to input of trace metals by water exchange over the sill in the upper part of the water column. In the deep water, less metal sulfide precipitation takes place due to depletion of trace metals, and the dilution of particulate metal concentrations by organic matter and by the chemogenic formation of calcite.     

Redox cycling of iron and manganese in sediments of the Kalix River estuary, Northern Sweden

Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fe_total and 84% of Mn_total). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m^–2 d^–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m^–2 d^–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m^–2 d^–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m^–2 d^–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm^–3 d^–1, respectively.     

Heavy metals distribution and fractionation in sediments of the Mahanadi River basin, India

Heavy metals distribution in core sediments, different size fractions of bed sediments (>212 urn, 90-212 jam, 63–90 urn, 53–63 urn, < 53 urn), and suspended sediments (>30 urn, 20–30 m, 10–20 urn, 2–10 urn, <2 m) have been discussed. Pb, Zn, and Cr have been accumulating in recent years in the sediments. Si, Al, Fe, Ca, and Mg dominate the bed and suspended sediment composition. Metals show increasing concentrations in finer sediments. Applying multivariate analysis to sediment composition, metals have been grouped into different factors depending upon their source of origin. Chemical fractionation studies on suspended and bed sediments show Fe, Zn, Cu, and Pb are associated with the residual fraction and Mn with the exchangeable fraction.