Heavy metals in stream sediments: Effects of human activities

The content of 11 heavy metals in the sediments of a stream system was determined by atomic absorption analysis. Geochemical phases were investigated using a sequential extraction scheme, and bulk contents were assessed with a single HNO₃ extraction. Certain heavy metals were associated with different geochemical phases. Co, Mn, and Ba concentrated primarily in the carbonate and Mn phases, while all the remaining metals concentrated in the Fe and remnant phases. Features located along the stream system influenced the content of heavy metals. Results from the geochemical phases indicated Cu, Pb, Zn, Cd and Ag were emitted by one landfill, while Cd, Ba, and Ag were emitted by a second landfill. A wastewater treatment facility appeared to emit Ni and Cu. A stream draining a reservoir and joining the study stream resulted in dilution of the heavy metals in the sediments. A populated area along the study stream appeared to emit Mn. The single HNO₃ extraction procedure is quicker to perform than the sequential extraction but does not indicate the phase associations.     

Distribution and immobilization of heavy metals in Pliocene aquifer sediments in Wadi El Natrun depression, Western Desert

The Pliocene aquifer receives inflow of Miocene and Pleistocene aquifer waters in Wadi El Natrun depression. The aquifer also receives inflow from the agricultural activity and septic tanks. Nine sediment samples were collected from the Pliocene aquifer in Wadi E1 Natrun. Heavy metal (Cu, Sr, Zn, Mn, Fe, Al, Ba, Cr, Ni, V, Cd, Co, Mo, and Pb) concentrations of Pliocene aquifer sediments were investigated in bulk, sand, and mud fractions. The determination of extractable trace metals (Cu, Zn, Fe, Mn, and Pb) in Pliocene aquifer sediments using sequential extraction procedure (four steps) has been performed in order to study environmental pathways (e.g., mobility of metals, bounding states). These employ a series of successively stronger chemical leaching reagents which nominally target the different compositional fractions. By analyzing the liquid leachates and the residual solid components, it is possible to determine not only the type and concentration of metals retained in each phase but also their potential ecological significance. Cu, Sr, Zn, Mn, Fe, and Al concentrations are higher in finer sediments than in coarser sediments, while Ba, Cr, Ni, V, Cd, Co, Mo, and Pb are enriched in the coarser fraction. The differences in relative concentrations are attributed to intense anthropogenic inputs from different sources. Heavy metal concentrations are higher than global average concentrations in sandstone, USEPA guidelines, and other local and international aquifer sediments. The order of trace elements in the bulk Pliocene aquifer sediments, from high to low concentrations, is Fe?>?Al?>?Mn?>?Cr?>?Zn?>?Cu?>?Ni?>?V?>?Sr?>?Ba?>?Pb?>?Mo?>?Cd?>?Co. The Pliocene aquifer sediments are highly contaminated for most toxic metals, except Pb and Co which have moderate contamination. The active soluble (F0) and exchangeable (F1) phases are represented by high concentrations of Cu, Zn, Fe, and Mn and relatively higher concentrations of Pb and Cd. This may be due to the increase of silt and clay fractions (mud) in sediments, which act as an adsorbent, retaining metals through ion exchange and other processes. The order of mobility of heavy metals in this phase is found to be Pb?>?Cd?>?Zn?>?Cu?>?Fe?>?Mn. The values of the active phase of most heavy metals are relatively high, indicating that Pliocene sediments are potentially a major sink for heavy metals characterized by high mobility and bioavailability. Fe–Mn oxyhydroxide phase is the most important fraction among labile fractions and represents 22% for Cd, 20% for Fe, 11% for Zn, 8% for Cu, 5% for Pb, and 3% for Mn. The organic matter-bound fraction contains 80% of Mn, 72% of Cu, 68% of Zn, 60% of Fe, 35% of Pb, and 30% of Cd (as mean). Summarizing the sequential extraction, a very good immobilization of the heavy metals by the organic matter-bound fraction is followed by the carbonate-exchangeable-bound fraction. The mobility of the Cd metal in the active and Fe–Mn oxyhydroxide phases is the highest, while the Mn metal had the lowest mobility.     

Transport and sediment–water partitioning of trace metals in acid mine drainage: an example from the abandoned Kwangyang Au–Ag mine area, South Korea

Transport and sediment–water partitioning of trace metals (Cr, Co, Fe, Pb, Cu, Ni, Zn, Cd) in acid mine drainage were studied in two creeks in the Kwangyang Au–Ag mine area, southern part of Korea. Chemical analysis of stream waters and the weak acid (0.1 N HCl) extraction, strong acid (HF–HNO₃–HClO₄) extraction, and sequential extraction of stream sediments were performed. Heavy metal pollution of sediments was higher in Chonam-ri creek than in Sagok-ri creek, because there is a larger source of base metal sulfides in the ores and waste dump upstream of Chonam-ri creek. The sediment–water distribution coefficients (K _d) for metals in both creeks were dependent on the water pH and decreased in the order Pb ≈ Al > Cu > Mn > Zn > Co > Ni ≈ Cd. K _d values for Al, Cu and Zn were very sensitive to changes in pH. The results of sequential extraction indicated that among non-residual fractions, Fe–Mn oxides are most important for retaining trace metals in the sediments. Therefore, the precipitation of Fe(–Mn) oxides due to pH increase in downstream sites plays an important role in regulating the concentrations of dissolved trace metals in both creeks. For Al, Co, Cu, Mn, Pb and Zn, the metal concentrations determined by 0.1 N HCl extraction (Korean Standard Method for Soil Pollution) were almost identical to the cumulative concentrations determined for the first three weakly-bound fractions (exchangeable + bound to carbonates + bound to Fe–Mn oxides) in the sequential extraction procedure. This suggests that 0.1 N HCl extraction can be effectively used to assess the environmentally available and/or bioavailable forms of trace metals in natural stream sediments.     

Partitioning of manganese,iron, copper,zinc, lead,cobalt, and nickel in black coatings on stream boulders in the vicinity of the Magruder mine,Lincoln Co., Georgia

Sequential digestions of Fe-Mn oxide coated boulders collected upstream and downstream from the Magruder mine, Lincoln Co., Georgia, indicate probable partitioning relationships for Zn, Cu, Pb, Co, and Ni with respect to Mn and Fe. Initial digestion with 0.1M hydroxylamine hydrochloride (Hxl) in 0.01M HNO₃ selectively dissolyes Mn oxides, whereas subsequent digestion with 1:4 HCl dissolves remaining Fe oxides.The results indicate that partitioning is not constant, but varies systematically with respect to the location of metal-rich waters derived from sulfide mineralization. Upstream from the mineralized zone Zn and Ni are distinctly partitioned to the Fe oxide component and Co and Cu are partitioned to the Mn oxide component. Immediately downstream from the mineralized zone, Mn oxides become relatively more enriched in Zn, whereas Fe oxides are relatively more enriched in Cu, Co, and Ni. Analytical precision for Pb is poor, but available data suggests it is more closely associated with Fe oxides.For routine geochemical surveys utilizing coated surfaces, a one-step digestion method is probably adequate. Parameters useful for detecting sulfide mineralization are metal concentrations normalized to surface area or various ratios (e.g. Zn/(Mn + Fe), Cu/Mn, Pb/Fe). Ratios can be obtained much faster, and at lower analytical costs than conventional analysis of stream sediment.     

Major and trace element anomalies in stream sediments of the Teign Valley Orefield

A detailed geochemical and sedimentological study of twenty-two bulk stream sediments in the Teign Valley of southwest Devon shows the influence of lithology, mineralization and contamination on such cumulative samples. K, Cu and Ni in stream sediments emerge as potential indicators of lithology. Ba and S values, as well as barytes concentrations, demonstrate the contribution of Ba, Zn and Pb mineral lodes, whilst Fe, S and heavy-mineral percentages emphasize that of Fe lodes and contamination. As, Pb and Zn anomalies are observed within Fe-oxide crusts giving evidence of Fe in the role of scavenger. High Mn values are attributed to precipitations of the metal derived largely from impregnations of the Culm.     

Composition of manganese nodules and manganese carbonates from Loch Fyne,Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn_47.7 Ca_45.1 Mg_7.2) CO₃. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.     

Chemical fractionation of transition elements in Pacific pelagic sediments

Partitioning of transition elements in Pacific pelagic sediments (35 samples) was performed by sequential chemical leaching with barium chloride/triethanolamine (easily extractable fraction), acidic cation exchange resin (carbonate phases), and hydroxylamine hydrochloride and dilute hydrochloric acid solutions (hydrous oxides). Residual metal percentages are highest in red-brown clays and siliceous ooze, intermediate in calcareous materials and low in micronodules (2 samples, > 125 μm): residual metal contents seem to be controlled predominantly by the rate of admixture of volcanoclastic materials. At higher bulk metal concentrations, the non-residual fractions of Mn, Cu, Ni and Zn generally increase both in red-brown pelagic clays and in siliceous ooze. Mn, Ni, and Co concentrations are mainly associated with the easily reducible fraction (0.1 M NH₂OH·HCl), whereas Fe, Cu, and Zn exhibit higher percentages in the hydrochloric acid soluble fractions (0.3 M HCl); Zn and Cu are associated to some extent with the carbonate phase, copper with the easily extractable fraction.     

Regional geochemical baseline concentration of potentially toxic trace metals in the mineralized Lom Basin,East Cameroon: a tool for contamination assessment

The distribution of trace metals in active stream sediments from the mineralized Lom Basin has been evaluated. Fifty-five bottom sediments were collected and the mineralogical composition of six pulverized samples determined by XRD. The fine fraction (<?150 µm) was subjected to total digestion (HClO₄?+?HF?+?HCl) and analyzed for trace metals using a combination of ICP-MS and AAS analytical methods. Results show that the mineralogy of stream sediments is dominated by quartz (39–86%), phyllosilicates (0–45%) and feldspars (0–27%). Mean concentrations of the analyzed metals are low (e.g. As?=?99.40 µg/kg, Zn?=?573.24 µg/kg, V?=?963.14 µg/kg and Cr?=?763.93 µg/kg). Iron and Mn have significant average concentrations of 28.325 and 442 mg/kg, respectively. Background and threshold values of the trace metals were computed statistically to determine geochemical anomalies of geologic or anthropogenic origin, particularly mining activity. Factor analysis, applied on normalized data, identified three associations: Ni–Cr–V–Co–As–Se–pH, Cu–Zn–Hg–Pb–Cd–Sc and Fe–Mn. The first association is controlled by source geology and the neutral pH, the second by sulphide mineralization and the last by chemical weathering of ferromagnesian minerals. Spatial analysis reveals similar distribution trends for Co–Cr–V–Ni and Cu–Zn–Pb–Sc reflecting the lithology and sulphide mineralization in the basin. Relatively high levels of As were concordant with reported gold occurrences in the area while Fe and Mn distribution are consistent with their source from the Fe-bearing metamorphic rocks. These findings provide baseline geochemical values for common and parallel geological domains in the eastern region of Cameroon. Although this study shows that the stream sediments are not polluted, the evaluation of metal composition in environmental samples from abandoned and active mine sites for comparison and environmental health risk assessment is highly recommended.     

Review of water and soil contamination in and around Salihli geothermal field (Manisa,Turkey)

The town of Salihli is situated in Gediz Graben in the western Anatolia. This region is important in terms of industry, mining, geothermal energy, water sources, and agricultural production. Geothermal flow and anthropogenic activities in Salihli threaten the surrounding environment due to the contamination of cold groundwater, surface water, and soil. The goal of the present study is to determine the environmental effects of the geothermal and anthropogenic activities in Salihli on soil, stream sediments, and water. Stream sediments and farm soil have been contaminated by substances derived from geothermal and industrial effluents. To this end, the quality review of the water was completed and the heavy metal levels in stream sediment samples were measured to determine the extent of contamination. The elements As, B, Br, Fe, and Ni are the major contaminants present in surface water and groundwater in the study area. The concentrations of these elements excess tolerance limits of international water standards. Gibbsite, K-mica, kaolinite, sepiolite, halite, sulfur, willemite, and Pb(OH)₂ might be precipitated as scales at low temperatures on the soil; this could be interpreted as a resultant from soil contamination. The concentrations of 17 elements (As, Ba, B, Cd, Co, Cr, Cu, Fe, Hg, Li, Mo, Mn, Ni, Pb, Sb, Sr, and Zn) were measured in samples from stream sediments and surface soils. In the study area, especially geothermal and anthropogenic activities give rise to environmental pollution.     

Geochemical comparison of waters and stream sediments close to abandoned Sb-Au and As-Au mining areas,northern Portugal

Waters from abandoned Sb-Au mining areas have higher Sb (up to 2138 μg L⁻¹), As (up to 1252 μg L⁻¹) and lower Al, Zn, Li, Ni and Co concentrations than those of waters from the As-Au mining area of Banjas, which only contain up to 64 μg L⁻¹ As. In general, Sb occurs mainly as SbO₃⁻ and As H₂AsO₄⁻. In general, waters from old Sb-Au mining areas are contaminated in Sb, As, Al, Fe, Cd, Mn, Ni and NO₂⁻, whereas those from the abandoned As-Au mining area are contaminated in Al, Fe, Mn, Ni, Cd and rarely in NO₂⁻. Waters from the latter area, immediately downstream of mine dumps are also contaminated in As. In stream sediments from Sb-Au and As-Au mining areas, Sb (up to 5488 mg kg⁻¹) and As (up to 235 mg kg⁻¹) show a similar behaviour and are mainly associated with the residual fraction. In most stream sediments, the As and Sb are not associated with the oxidizable fraction, while Fe is associated with organic matter, indicating that sulphides (mainly arsenopyrite and pyrite) and sulphosalts containing those metalloids and metal are weathered. Arsenic and Sb are mainly associated with clay minerals (chlorite and mica; vermiculite in stream sediments from old Sb-Au mining areas) and probably also with insoluble Sb phases of stream sediments. In the most contaminated stream sediments, metalloids are also associated with Fe phases (hematite and goethite, and also lepidocrocite in stream sediments from Banjas). Moreover, the most contaminated stream sediments correspond to the most contaminated waters, reflecting the limited capacity of stream sediments to retain metals and metalloids.     

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).     

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.     

Organic matter-metal interactions in Recent sediments: the role of humic substances

Atomic emission spectrographic analysis of the trace inorganic constituents of marine humic substances gave the following range of concentrations: Si, 200 ppm to > 2%; Al, 400 ppm to ~ 1%; Fe, 600–3000 ppm; Ca, 600 ppm to > 2%; Mg, 20–6000 ppm; Na, 600 ppm to > 2%; Ag, < 6–600 ppm; B, < 60–1000 ppm; Cu, 600–4000 ppm; Mn, 8–100 ppm; Mo, <20–3000 ppm; Ni, 100–1000 ppm; Pb, < 40–600 ppm; Sn, 40–600 ppm; Ti, < 20–2500 ppm; V, 20–200 ppm; Zn, 350–4500 ppm; Zr, < 60–500 ppm.Humic substances contain a sizeable portion of the Cu, Mo and Zn found in sediments, but are less important for Ni, Co and Pb, and are insignificant for the Mn, V and Fe content. The metals are mostly introduced into the humates during their diagenetic formation in sediment by dissolution of metals from various mineralogical phases. A precursor of the sedimentary humates, the polymeric organic material dissolved in interstitial water, contains most of the Cu and Zn, about half of the Ni, Fe and Co, and very little of the Mn found in interstitial water. Comparison of the data on humates with that obtained by H₂O₂ treatment of sediments indicates that Cu, Zn and possibly most of the Mo are associated with organic matter, but that Ni and Co are associated with sulfides.     

Partitioning of heavy metals in surface Black Sea sediments

Bulk heavy metal (Fe, Mn, Co, Cr, Ni, Cu, Zn and Pb) distributions and their chemical partitioning, together with TOC and carbonate data, were studied in oxic to anoxic surface sediments (0–2 cm) obtained at 18 stations throughout the Black Sea. TOC and carbonate contents, and available hydrographic data, indicate biogenic organic matter produced in shallower waters is transported and buried in the deeper waters of the Black Sea. Bulk metal concentrations measured in the sediments can be related to their geochemical cycles and the geology of the surrounding Black Sea region. Somewhat high Cr and Ni contents in the sediments are interpreted to reflect, in part, the weathering of basic-ultrabasic rocks on the Turkish mainland. Maximum carbonate-free levels of Mn (4347 ppm), Ni (355 ppm) and Co (64 ppm) obtained for sediment from the shallow-water station (102 m) probably result from redox cycling at the socalled ‘Mn pump zone’ where scavenging-precipitation processes of Mn prevail. Chemical partitioning of the heavy metals revealed that Cu, Cr and Fe seem to be significantly bound to the detrital phases whereas carbonate phases tend to hold considerable amounts of Mn and Pb. The sequential extraction procedures used in this study also show that the metals Fe, Co, Ni, Cu, Zn and Pb associated with the ‘oxidizable phases’ are in far greater concentrations than the occurrences of these metals with detrital and carbonate phases. These results are in good agreement with the recent studies on suspended matter and thermodynamic calculations which have revealed that organic compounds and sulfides are the major metal carriers in the anoxic Black Sea basin, whereas Fe-Mn oxyhydroxides can also be important phases of other metals, especially at oxic sites. This study shows that, if used with a suitable combination of the various sequential extraction techniques, metal partitioning can provide important information on the varying geological sources and modes of occurrence and distribution of heavy metals in sediments, as well as, on the physical and chemical conditions prevailing in an anoxic marine environment.     

A comparison of the early diagenetic environment in intertidal sands and muds of the Manukau Harbour,New Zealand

The early diagenetic environment of intertidal sandy sediments (sands) and muddy sediments (muds) is described and compared from two cores taken from an unpolluted part of the Manukau Harbour, New Zealand. Extraction techniques characterized the form of the trace elements (Fe, Mn, S, C, Pb, Zn, Cu) at different depths in the sediment. Dissolved forms of Fe, Mn, and S were measured in interstitial water. Nonresidual metal concentrations, humic acid, FeS, and FeS₂ are an order of magnitude higher in the muds than in the sands because of dilution by unreactive sand particles. Muds contain a larger proportion of metals in the mobile fractions; exchangeable (Mn), carbonate (Mn, Fe, Zn), and easily-reducible oxide (Fe, Mn, Zn, Pb). This is due to greater surface area (for Mn adsorption); the favorable conditions for MnCO₃, FeCO₃, and FeS precipitation; and higher concentrations of easily reducible iron oxide and humic acid. Therefore, compared to the sands, muds are more important as reservoirs for toxic metals, both in terms of quantity and availability. At either site there was very little difference between the forms of Zn, Pb or Cu identified by sequential extraction as sediments changed from oxic to anoxic conditions. One reason for this is that the amounts and proportions of some of the important components that bind metals, viz., amorphous iron hydrous oxides, humic acids, and FeS₂, do not change much. Other components that do change with redox conditions, for example, manganese phases and FeS, are only minor components of the sediment. Redox conditions, then, have relatively little effect on trace-metal partitioning in the sediment matrix of these unpolluted sediments.     

Colloidal and truly dissolved metal(oid) fractionation in sediment pore waters using tangential flow filtration

The partitioning of trace metal(oid)s between colloidal and “truly” dissolved fractions in sediment pore waters is often overlooked due to the analytical challenge; indeed, only small volumes are available and filtration membranes are rapidly clogged. Moreover, metal(oid)s are subject to co-precipitate with Fe. In this study, tangential flow filtration (TFF) was assessed for the fractionation of Fe, Mn, Cu, As, Co, Ni, Zn and Cd in sediment pore waters with a 5 kDa cut-off size membrane. Five natural sediments were collected and used for different tests. Results on blank samples showed that this technique was appropriate for Fe, Mn, Co, Zn, As and Cd. Although the applied concentration factors (CF) were low (<7.4) due to the small available volume of pore waters (50 mL), it was shown that colloidal concentrations obtained from the TFF procedure were similar whatever the applied concentration factor. The mass balance approach showed satisfying results (100 ± 25%) for Mn, Co, Zn and As. Mass balances were higher than 130% and highly variable for Cd, Ni and Cu. For Fe, mass balance was reproducible but low (71 ± 10%), probably due to sorption of positively charged Fe oxides on the membrane. Applying this method to five contrasting metal(oid)-contaminated sediments, it was shown that Mn, As, Co and Fe were mainly present in the “truly” dissolved phase (<5 kDa). This technique is a necessary step to assess sediment toxicity and bioavailability of metal(oid)s and could be of great interest for emergent pollutants such as nanometals.     

The effects of the San Francisco Bay plume on trace metal and nutrient distributions in the Gulf of the Farallones

The distributions of particulate elements (Al, P, Mn, Fe, Co, Cu, Zn, Cd, and Pb), dissolved trace metals (Mn, Fe, Co, Cu, Zn, and Cd), and dissolved nutrients (nitrate, phosphate, and silicic acid) were investigated in the Gulf of the Farallones, a region of high productivity that is driven by the dynamic mixing of the San Francisco Bay plume, upwelled waters, and California coastal surface waters. Particulate metals were separated into >10 and 0.4-10 μm size-fractions and further fractionated into leachable (operationally defined with a 25% acetic acid leach) and refractory particulate concentrations. Dissolved metals (< 0.4 μm pore-size filtrate) were separated into colloidal (0.03-0.4 μm) and soluble (<0.03 μm) fractions. The percent leachable particulate fractions ranged from 2% to 99% of the total particulate concentration for these metals with Mn and Cd being predominantly leachable and Fe and Al being predominantly refractory. The leachable particulate Pb concentration was associated primarily with suspended sediments from San Francisco Bay and was a tracer of the plume in coastal waters. The particulate trace metal data suggest that the leachable fraction was an available source of trace metal micronutrients to the primary productivity in coastal waters. The dissolved trace metals in the San Francisco Bay plume and freshly upwelled surface waters were similar in concentration, with the exception of Cu and Co, which exhibited relatively high concentrations in plume waters and served as tracers of this water mass. The dissolved data and estimates of the plume dynamics suggest that the impact of anthropogenic inputs of nutrients and trace metals in the San Francisco Bay plume contributes substantially to the concentrations found in the Gulf of the Farallones (10-50% of estimated upwelled flux values), but does not greatly disrupt the natural stoichiometric balance of trace metal and nutrient elements within coastal waters given the similarity in concentrations to sources in upwelled water. In all, the data from this study demonstrate that the flux of dissolved nutrients and bioactive trace metals from the San Francisco Bay plume contribute to the high and relatively constant phytoplankton biomass observed in the Gulf of the Farallones.     

Surface metal enrichment and partitioning of metals in a dated sediment core from a Norwegian fjord

A 24-cm long sediment core from an oxic fjord basin in Ranafjord, Northern Norway, was sliced in 2 cm sections and analysed for As, Co, Cu, Ni, Hg, Pb, Zn, Mn, Fe, ignition loss and Pb-210. Partitioning of metals between silicate, non-silicate and non-detrital phases was assessed by leaching experiments, in an attempt to understand the mechanisms of surface metal enrichment in sediments. Relative to metal concentrations in sediments deposited in the 19th century, metals in near surface sediments were enriched in the following order: Pb > Mn > Hg > Zn > Cu > As > Fe. Cobalt and Ni showed no enrichment. The non-detrital fraction of Cu, Pb, Mn and Zn was significantly higher in the upper 10 cm than at greater depth in the core. This corresponds to sediments deposited since 1900, when mining activities started in the area. The enrichment of Cu, Pb and Zn is assumed to be mainly a result of mining, while Mn is apparently enriched in the surface due to migration of dissolved Mn and precipitation in the oxic surface layer. Elevated concentrations of As and Fe in the upper 4 cm are presumably due to discharges from a coke plant and an iron works respectively. The excess Hg present in the near surface sediments is tightly bound, either in coal particles or ore dust introduced by local industry, or via long distance transport of atmospheric particles. Calculations of metal flux to the sediments indicate an anthropogenic flux of Zn equal to its natural flux, while the flux of Pb shows a threefold increase above natural input.     

Comparison of metal homogeneity in grab,quartered, and crushed — sieved portions of stream sediments and metal content change resulting from crushing — sieving activity

Restricted grain size sediment samples were collected along two streams. Metal content in some samples may have been influenced by landfill emissions. Each sample was divided into a grab portion, a quartered portion, and a portion crushed and sieved to a smaller size and then quartered. A duplicate sample from each of these portions was extracted. The Cu, Pb, Zn, Co, Ba, Fe, Mn, and Ca quantities were determined for each duplicate sample. Relative standard deviation was used to reflect homogeneity of metal content. Metal occurrence represented speciated metals or major components of chemical phases. Results indicated that variation of metal content among portions was uniform and did not vary as a function of absolute metal quantity. Homogeneity was similar in the same size grab and quartered samples. A more homogeneous metal state was displayed by the crushed and sieved sediments. However, this activity enriched softer chemical phases and associated speciated metals. It was concluded that sediments need not be quartered to obtain a better homogeneity of metal distribution and that field samples should not be crushed and sieved prior to chemical analyses. Assessment of sediments affected by metal emission sources must include a knowledge of metal homogeneity in individual samples.     

Mobility of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric O2: an experimental study

 The major aim was to increase our knowledge on the behaviour of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric oxygen. Samples of this type of sediment collected in a previous investigation at eight sites in western Finland were digested in HClO₄-HNO₃-HCl-HF at 200  °C and in HCl:HNO₃:H₂O at 95  °C (aqua regia), and subjected to extractions with ammonium acetate and hydrogen peroxide. Metals and S in the leachates were determined with ICP-AES. The results of the chemical analyses are compared with previously reported experimental data. The concentrations of Al and Fe in the sulphide-bearing fine-grained sediments are about 7% and 5%, respectively. Of the trace metals studied, Mn is most abundant followed in decreasing order by V>Cr>Ni>Cu>Co. On oxidation of the sediments, high proportions of Co, Mn and Ni, intermediate proportions of Cu but low proportions of Fe, Al, Cr and V are released. The extent of the release of a metal on oxidation is controlled either by (1) the level to which the pH of the sediments drops on oxidation (Al, Cu, Cr, V), (2) the amount of the metal associated with easily reduced phases (metal sulphides) in the sediments (Ni, Co) or (3) the sum of the amount associated with reduced phases and adsorbed on soil compounds (Mn). No control of the release of Fe on oxidation of the sediments was identified. Based on the results of the study it is argued that artificial drainage and the subsequent oxidation of sulphide-bearing sediments will result in extensive leaching of Co, Mn and Ni, moderate leaching of Cu and limited leaching of Cr and V into drainages. The major elements, Fe and Al, have the potential to be mobilised and leached in large amounts, though the proportions mobilised/leached will remain low. It is suggested that the identification of sulphide-bearing sediments with a high potential of metal release should be based on determination of metals in easily mobilised reduced compounds (dissolved e.g. in H₂O₂) and of the level to which the pH of the sediments drops on oxidation. Received: 16 October 1997 · Accepted: 9 March 1998