Early diagenetic processes aspects controlling the mobility of dissolved trace metals in three riverine sediment columns

The behaviour of Mn, Fe, Co, Zn, Cd, Pb and Ni has been studied during early diagenesis in three different riverine sediments (Spierre, Lys and Sheldt). For that purpose (1) pore waters were extracted from sediment cores by centrifugation under nitrogen and further analyzed for the determination of total dissolved metal concentrations and (2) DET and DGT probes have been deployed in situ for the determination of high resolution profiles of labile and total dissolved metal concentrations. Furthermore, sulfidization processes have been examined; they revealed a production of pyrite near the water-sediment interface at Helkijn and Wervik sampling sites, probably due to a partial re-oxidation of reduced sulphur species. In Spierre sediments, where Eh values are the most negative, pyrite production should be mainly due to strict anaerobic processes. Concentrations of AVS in Spierre sediments are also very high and result in low TI values and low trace metal concentrations in the pore waters. Otherwise, in Wervik sediments, the low pH values combined to a TI value close to 0 results in the highest observed dissolved trace metal levels. DOS remains low at the three sites, since it does not exceed 0.4. In Wervik and Helkijn, the limitation is probably due to low sedimentary inputs of sulphate. In Spierre, sulphate is never exhausted in the pore water, suggesting a limitation of the DOS by a lack of bio-degradable organic matter. Values of Cd, Cu and Pb DGT concentrations remain low in pore waters whatever the site, due to their strong affinity with the reduced sulphur pool. It has also been demonstrated that the labile fractions of Pb and Cd are the lowest and do not exceed 0.5, while Co and Ni are the most available metals.     

Partitioning of trace metals between dissolved and particulate phases in a typical backwater system of Kerala,India

Concentrations of dissolved and particulate trace metals (Ni, Pb, Zn and Mn) and their partitioning behaviour between the dissolved and particulate phases in a typical backwater system of Kerala, viz. the southern upstream part of Cochin Estuarine System (South India), have been studied. Spatial and temporal variations of trace metals in the dissolved and particulate phases have been discussed with special reference to pH, dissolved oxygen, salinity and suspended particulate matter. The distribution and partitioning behaviour of trace metals in the water column were found influenced by the presence of a salinity barrier across the backwater system and also by the massive use of pesticides and chemical fertilizers in the vast area of agricultural land near the backwater system. Lack of proper flushing of the backwaters, which receive large amount of trace metals through the application of pesticides and agro‐chemicals, due to the presence of the salinity barrier has significantly affected the water quality of the area.     

Electrochemical speciation of trace metals in sea water

Various approaches, such as bioassays, computer-assisted modelling and direct measurement following physical separation are currently being used to investigate the speciation of trace metals in sea water. The electrochemical techniques used successfully as a necessary prerequisite for the experiments involved include conventional polarography, anodic stripping voltammetry (ASV) and potentiometry. Differential pulse anodic stripping voltammetry (DPASV) using mercury film electrodes enables direct studies in ultratrace levels present in non-contaminated ocean waters.By varying the conditions of the sample chemistry and electroanalysis it is possible to characterize metal-organic interactions. This is demonstrated in the case of natural sea water samples subjected to ASV diagnosis. Differences in the Pb and Cu values yielded for Baltic waters by two methods based on DPASV and AAS are discussed with regard to speciation.An analysis of the existing literature is used to briefly summarize the needs of future research. Important problems requiring a more precise quantitative analysis include the adsorption of organics on electrodes and the kinetics and thermodynamic constants of chelates with special regard to the physico-chemical nature of metal-humic substances. The introduction of new and improved electroanalytical techniques and equipment for speciation studies is strongly recommended.     

Heavy metals in animals of Lake Balaton

Hg, Cd, Cu, Pb, Zn, Fe and Mn concentrations were measured in Chironomidae larvae, Crustacea plankton, as well as in various organs of mussels and fishes collected from the open water area of Lake Balaton. The values were comparatively low. However, there were significant differences in the metal concentrations of species and tissue.Most Cd was found in the gill of Unio pictorum L., most Pb, Zn and Mn in the gill of Anodonta cygnea L., most Cu in Crustacea plankton and in the liver of Abramis brama L., and most Hg and Fe in Chironomidae larvae. Low concentrations occurred in fishes, the lowest in the flesh of Stizostedion lucioperca L.Accumulation of metals in organs as compared with their concentration in the lake water was in the range of 3.4 × 10²−2.6 × 10³ for Hg; 7.0 × 10²−6.8 × 10³ for Cd; 3.3 × 10²−9.7 × 10³ for Cu; 6.9 × 10²−8.1 × 10³ for Zn; 1.5 × 10³−2.4 × 10⁴ for Pb; 3.5 × 10²−3.1 × 10⁴ for Fe; and 5.0 × 10¹−3.5 × 10⁵ for Mn.     

Concentration and fate of trace metals in Mekong River delta

In the Mekong River delta and its associated coastal zone trace elements concentrations (Cd, Cu, Ni and Pb) were measured in the dissolved phase (DP) during dry (March 1997) and wet (October 1997) seasons. As, Co, Cr, Ni, Pb, and Al were also measured in suspended matter (SM) and total and organic carbon, trace elements (Cd, Cr, Cu, Hg, Mn, Ni, Pb, Zn) and macro elements in superficial sediments (S). Trace metal concentrations in DP and SM during the contrasting hydrological conditions were generally found within the range observed for uncontaminated environment. The average DP concentrations (nM) in the river for March and October are: Cd 0.03 and 0.09, Cu 15 and 14, Ni 7.8 and 8.4, Pb 0.51 and 0.50, respectively. In general there is no significant difference between the concentrations observed during dry and wet season. The evolution of the DP trace metal concentration in the surface water within the salinity gradient suggests no noticeable exchange between the particulate and dissolved phase. This result is in good agreement with those observed in most plume structures studied so far. The average concentrations in the SM (microg/g) (March, October) at the river end-member are: As (24; 11), Co (17; 9), Cr (49; 29), Ni (32; 18), Pb (42; 19) and Al (113,000; 67,000), respectively. All trace elements show higher concentrations in March than in October, with an average increase of two times. This is essentially related to grain size effect since smaller particles were supplied during dry season. These differences are not reflected in the mixing zone, which integrates the seasonal variations. The concentration of major elements (C total, C organic, Si, Al, Ca, K, Fe, Mg, Ti), trace elements (Pb, Zn, Cu, Ni, Mn, Cr, Cd, Hg) in superficial sediments, show similar values during the two seasons and does not show any important variation with depth, indicating either a very fast sedimentation rate and/or the absence of any significant contamination.     

Partitioning of trace metals before and after biological removal of metals from sediments

Metal removal by biological solubilization in three strongly contaminated sediments was carried out in a two-liter stirred bioreactor. Biological treatment yielded metal removal efficiencies in the range of 11-30%, 43-57%, 60-79%, 61-90%, 18-21%, 0-10% for Pb, Cu, Zn, Cd, Ni and Cr, respectively. The treated sediments were then rinsed with a NaCl solution (0.5 M), resulting in an increase by nearly 47% in Pb removal for the three sediments, while for other metals (Cu, Zn, Cd, Ni, Cr), the NaCl rinse did not seem to allow any significant increase in metal solubilization. A standard procedure of sequential selective extraction (SSE) was applied to the sediments before and after each treatment. With regard to Pb, Zn and Cd, the carbonate bound fractions (2/3 sediments) represented 18-42% of metals prior to treatment, while the iron and manganese oxides bound fraction constituted 39-60% of metals for the three sediments. Between 90 and 100% of Pb, Zn and Cd removed by the process came from the fractions bound to carbonates and from those bound to Fe and Mn oxides. The organic matter and sulfide bound fractions contained 65-72% of total Cu present before treatment and the process removed, on average, 63% Cu present in this fraction. In contrast, Ni and Cr were found mainly in the residual fractions (50-80%). Finally, this biological treatment did not solubilize Cr appreciably, while removal of Ni mostly originated from the carbonate and Fe/Mn oxides fractions (70-80%).     

Seasonal variation of psychrotrophic bacteria in sediment from Lake Ontario

Bacteria were isolated from sediment samples obtained from the Bay of Quinte, Lake Ontario, at four different seasons. Isolation of the bacteria was accomplished at 0°C and 20°C and the growth of randomly-selected isolates at each of these temperatures was assessed. The bacteria were identified using miniaturized identification methods and Pseudomonas and Flavobacterium were the most frequently isolated genera. Significant differences were found in the numbers of bacteria in the sediment samples taken at different sampling times and incubated at different temperatures. The numbers isolated with incubation at 20°C were always the same or higher than those isolated from the same sample at 0°C. Almost all bacteria isolated at 0°C were capable of growth at 20°C. The greatest population diversity occurred in the sediment samples collected when the in situ sediment temperatures were low. Distinct changes in population composition were noted at the different sampling times. The majority of the bacteria isolated were capable of growth at 0°C, so that a large psychrotrophic population was present throughout the year in the sediment.     

Species of dissolved metals derived from oligotrophic hard water

By fractioning of dissolved organic carbon (DOC) and of associated metals Na, K, Mg, Ca, Al, Fe, Mn, Ni, Cr, Cu, Pb, Cd, and Zn according to the molecular sizes by means of gel chromatography in several stages, it could be shown that all metals, even the alkaline and alkaline earth metals, are, to a measurable degree, present in chelated form. This type of association covers 97.3% with Pb, 94.6% with Al, 91.5% with Cr, 82.2% with Fe of the total concentrations of each metal mentioned. About 69% of all metal chelates are represented by Mg-compounds. This may be caused by pre-treatment procedures, nevertheless the Mg-concentrations of the different DOC-fractions indicating to be one regulating factor for the uptake of other metals in the studied hard water. The chelated form was also obtained with Mn, Cd, Zn, and Mg, while with Cu, Ni, Na, Ca, and K there is an abundance of ionic forms.The metal distribution within the different molecular size fractions of the DOC proves the existence of specific distribution pattern for Pb and Mn: Pb is preferably chelated by macromolecular substances, whereas Mn combines mainly with minor ones. Cr seems to behave similar as Pb. Regulation' mechanisms for the different metal distribution patterns within the DOC-fractions as well as ecophysiological aspects of the results are discussed.     

Manganese flux associated with dissolved and suspended manganese forms in Lake Fukami-ike

Redissolved, particulate and sedimentary managanese were studied in the anoxic hypolimnion of the small monomictic Lake Fukami-ike in central Japan. The amounts of particulate and dissolved manganese in the water column were observed. The release of dissolved managanese starts gradually beginning in March. DMn reaches especially high levels of 93 mgMn m⁻² d⁻¹ from the end of May to the end of June calculated from the gradient of a regression formula for the daily change in DMn. The rate of accumulated PMn is 0.64 mgMn m⁻² d⁻¹ from the end of July calculated from the gradient of a regression formula for the daily change in PMn.An accumulation of PMn and an associated decrease in dissolved organic carbon (DOC) were observed at the transition zone of oxic and anoxic layers. These facts seem to suggest that the DOC decrease involves the consumption of DOC as an electron donor by bacterial catalysis for the reduction of MnO₂. The upward and downward DOC fluxes, 0.320 mmolC m⁻² d⁻¹, were calculated by the mean gradient values of the upward and downward DOC concentrations. The mean DOC flux was calculated by both the mean gradient DOC and the vertical diffusion coefficient (0.0304 m⁻² d⁻¹). Manganese-reducing bacteria could contribute as much as 24% to the DOC decrease in the oxic and anoxic layers, considering bacterial assimilation efficiency (64%). Vertical diffusion Mn flux from the interstitial water to the hypolimnion is then assumed to be 2 mgMn m⁻² d⁻¹.Mn for the vertical eddy diffusion flux, the vertical diffusion flux from interstitial water of the bottom sediment, the sinking flux and microbiological Mn flux were obtained, and the biogeochemical managanese cycle in Lake Fukami-ike was calculated. DMn flux in the oxic and anoxic layers by manganese-reducing bacteria is 0.004 gMn m⁻² d⁻¹, a value corresponding to 10% of DMn flux.     

Lead concentration profiles in lead-210 dated Lake Ontario sediment cores

Lead concentrations were measured in sediment cores from four sites distributed among the three major sedimentary basins — Niagara, Mississauga and Rochester — of Lake Ontario for which sedimentation rates had been previously determined by ²¹⁰Pb dating.Around 90% of the total lead present in fine-grained surface sediments was removed by CH₃CO₂H/NH₂OH · HCl leaching, concentrations ranging from 137 μg/g in surface sections to a constant background of 12–13 μg/g at unpolluted depths. Lead-210 dating indicated that increases in lead concentrations commenced ca. 1850–1875 with 5, 10, 35 and 50% of the total “excess” lead inventory in the sediment column being assigned to the pre-1900 period and successive 25-year intervals during the 20th Century, respectively. Anthropogenic inputs of lead from such sources as the combustion of leaded gasoline and coal are responsible for these increases.About 10 μg/g lead remained in the sediment residue after leaching. The total natural lead flux to the sediments ranged from 0.4–1.3 μg/cm²/yr while “excess” lead of anthropogenic origin varied from 1.2–6.7 μg/cm²/yr and totalled 0.5–1.5 g/m² at the four sites.Various potential modes of introduction of anthropogenic lead and of ²¹⁰Pb to the lake are considered in conjunction with the ratio of Pb/²¹⁰Pb fluxes to the sediment.     

Carcinogenic and genotoxic activity of extracts from contaminated sediments in western Lake Ontario

In order to investigate the putative association between chemical contamination in western Lake Ontario and high prevalences of fish tumors, sediments from Hamilton Harbour and Oakville Creek in Lake Ontario and reference sites in non-polluted areas of Ontario, Canada were collected and extracted for organic contaminants. Sediment extracts from Hamilton Harbour had the highest concentrations of polychlorinated biphenyls and organochlorine insecticides (ppb) and contained very high concentrations of polynuclear aromatic hydrocarbons (ppm); although the levels of these compounds varied widely with sampling location in the harbor. A sediment extract from Hamilton Harbour was mutagenic in the Ames bacterial assay, both with and without microsomal activation. High levels of aromatic DNA adducts were induced in cultured mouse C3H1OT1/2 cells after in vitro exposure to Hamilton Harbour sediment extract. In two separate carcinogenicity experiments involving a sac fry microinjection assay with rainbow trout (Oncorhynchus mykiss), Hamilton Harbour sediment extract induced hepatocellular carcinomas in fish. No hepatic neoplasms were observed in fish that had been treated with sediment extract from Oakville Creek, or with extract from a reference sediment. The significance of these results is discussed in relation to the distribution of neoplasms in feral fish within western Lake Ontario.     

Relationship between dissolved organic and inorganic compounds in tributaries of the Lake Baikal

It was shown that the balance between organic and inorganic compounds is mostly conditioned by watershed size and relief, rather than chemistry. The rise and fall of dissolved organic carbon concentration are irreversely proportional to those of acid neutralizing capacity and follow the changes in water flowpaths. This relationship was used to distinguish between dissolved matter sources, and to characterize quantitatively and qualitatively their contribution to surface water chemistry. The proposed approach has restricted applicability to the watersheds composed of sedimentary materials and to the watersheds with high percentage of wetlands. The applicability of the approach is also limited to a variety of environmental conditions. Big watersheds should be divided into lower order subcatchments to reduce uncertainty in interpretation of results. In small and medium watersheds, the proposed approach can be used for predicting water chemistry under different environmental conditions and for tracing contaminants.     

Kidney and liver levels of some major, minor and trace elements in two Ontario communities

The contents of Ag, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, P, Pb, Se, Sr, Th, Ti and Zn in 143 autopsied liver and kidney specimens from two Ontario communities (Kingston and Ottawa) were determined using the techniques of inductively-coupled plasma--atomic emission spectrometry, and electrothermal atomization--atomic absorption spectrometry coupled with hydride evolution (As, Se), reduction--aeration (Hg), or solvent extraction (Pb). The majority of samples came from individuals older than 50 y. In general, the data for the various elements were independent of age or sex but showed some dependence on location for elements such as Cu, Fe, K, Mg, Mn, Na, P, Se and Zn. Despite these differences the elemental values of the liver and kidney samples from both the communities were within the normal range.     

Short-term variability of dissolved trace element concentrations in the Marne and Seine rivers near Paris

The concentrations of dissolved trace elements (Li, B, Mn, Cu, As, Rb, Sr, Mo, Cd, Ba, Pb) in the Marne and Seine rivers in the Paris urban area were monitored over a 2-year period. The resulting data indicated moderate contamination of waters by the most toxic elements (Cu, As, Cd and Pb). The River Marne upstream and the River Seine downstream of the city of Paris displayed similar concentrations. However higher fluxes of trace elements were observed in the Seine than in the Marne due to their different discharges. Li, B, Rb, Sr and Ba concentrations were correlated with river discharge and concentrations were higher during high river flow. This was interpreted as a dilution by discharge from a major natural or anthropogenic source. Mn, Cu, Mo, Cd and Pb concentrations were not correlated with discharge. Dissolved Mn, Cu and Cd increased rapidly in summer, whereas the concentration of Mo decreased. These variations were attributed to redox processes. During summer when the dissolved oxygen concentrations decrease, Mn, Cu, Cd and Pb are released into solution whereas Mo is immobilised. Like metals, variations in arsenic contents were not linked with discharge. Its similarity with phosphate distribution suggests similar controls involving phytoplankton uptake and release from sediments through organic matter mineralization.     

Dynamics of dissolved oxygen during algal bloom in Lake Kasumigaura, Japan

Dynamics of dissolved oxygen during an algal bloom were studied in Lake Kasumigaura. Great amounts of oxygen arose from photosynthesis, and the concentration of dissolved oxygen reached 190% of saturation at 12 h. The majority of the dissolved oxygen produced was liberated into the atmosphere or consumed by microorganisms. Only minor fractions were transported into the dysphotic zone due to the low eddy diffusion coefficient in deeper waters of the euphotic zone.     

Flow-injection sample preconcentration for ion-pair chromatography of trace metals in waters

Selected trace transition metal ions have been determined in an FIA/HPLC hyphenated system using on-line preconcentration on cellulose functionalised sorbent Cellex P. For HPLC separation ion-pair chromatography was employed with spectrophotometric detection at 510 nm using post-column derivatisation with PAR. Favourable kinetic conditions of sorption and elution as well as optimisation of hyphenated system allowed to obtain detection limits at sub-microgL(-1) level at 25 min preconcentration time. The developed method was employed for determination of Co(II), Ni(II), Cd(II) and Mn(II) in river water with reasonable agreement of obtained results with electrothermal AAS determination.     

The determination of trace metals in sea-water using cathodic stripping voltammetry

Procedures have recently been developed to determine Fe, U, V, Cu, Zn, Mo, Ni and Co in water by cathodic stripping voltammetry (CSV) preceded by adsorptive collection. The procedures, reaction mechanism and possible interferences are discussed here. The potentialities of this technique for the investigation of metal speciation are briefly outlined.     

Addition of trace metals increases denitrification rate in closed marine systems

We investigated the effect of trace metals (Fe, Mn, Cu, Zn and Mo) on the denitrification unit at the Montreal Biodome. Two dosages of the five trace metals were tested on a denitrifying bacterial population which was extracted from the denitrification unit and cultured in 250 mL chemostats with artificial seawater. The low dosage showed a 20% increase in the denitrification rate whereas the high dosage had a more pronounced effect with a 250% increase. No increase in bacterial growth was observed, suggesting that the trace metals had an effect on the denitrification activity. When the trace metals were tested separately, only iron had a significant effect similar to the increase in the denitrification rate observed when the five trace metals were added. The combination of Fe and Mn caused a small but significant increase compared to the five trace metals. We then tested the effect of adding Fe, Mn and Cu to the denitrification unit at the Montreal Biodome. A high dosage of these trace metals showed a 250% increase in the denitrification rate, which went from 200 to 700 g NO(x)-N/d. Our results showed that the addition of trace metals is crucial for denitrification activities.     

Mobile and bound forms of trace metals in sediments of the lower ganges

Mobile and bound trace metals associated with sediment components (viz. exchangeable, carbonate, organic, Fe/Mn oxide and residual fractions) were determined at five locations on the River Ganges in the lower reaches. In the exchangeable phase, 5–22% of Pb, 5–14.4% of Cr, 3–16.4% of Cd, 3–16% of Zn and 1–13.5% of Cu were found, and in the carbonate phase 73–87% of Zn, 38–41% of Cd, 13–27% of Ni and 3–10.1% of Pb were found. The Fe/Mn oxide phase retained about 79–83% of Mn, 30–40% of Cr and Fe, 22–25% of Cu, 14–16% of Ni and 9–11% of Pb. In the organic phase about 36–47% of Cd, 22–28% of Cu and 10–15% of Pb were found. The order of release of metals was Cd > Cr > Pb > Cu > Zn > Ni > Mn > Fe, and the order of adsorption characteristics of most of the mobile metal fractions was Fe/Mn oxide > organic > clay. Correlations of the physico-chemical parameters with adsorption characteristics were also determined and a good correlation (r = 0.7) of cation exchange capacity with the clay fraction was found. I_geo (geoaccumulation indices) of metals in the sediments were also evaluated. Results showed a considerable enrichment of trace metals in the sediment phase at almost all the sites.     

Dredging-related mobilisation of trace metals: a case study in The Netherlands

Mobilisation of contaminants is an important issue in environmental risk assessment of dredging projects. This study has aimed at identifying the effects of dredging on mobilisation of trace metals (Zn, Cu, Cd and Pb). The intensities and time scales of trace metal mobilisation were investigated during an experimental dredging project conducted under field conditions. The loss of contaminated dredge spoil is mainly reflected by increasing levels of trace metals in the suspended matter, dissolved trace metal concentrations in the water column are not significantly influenced by the dredging activities. This indicates a strong binding mechanism of trace metals to the solid phase or a fast redistribution over sorptive phases in response to oxidation of e.g. trace metal sulphides. Given the differences in levels of reactive phases (Mn, Fe, sulphides and organic matter) between the riverine suspended matter and the sediments, changes in the levels of these parameters in the suspended matter upon dredging may give information on the processes influencing the behaviour of trace metals and on the potential loss of sediment during dredging operations. Therefore, we recommend to routinely measure these parameters in studies on contaminant behaviour related to dredging activities.