Heavy metal anomalies in the Tinto and Odiel River and estuary system,Spain

The Tinto and Odiel rivers drain 100 km from the Rio Tinto sulphide mining district, and join at a 20-km long estuary entering the Atlantic Ocean. A reconnaissance study of heavy metal anomalies in channel sand and overbank mud of the river and estuary by semi-quantitative emission dc-arc spectrographic analysis shows the following upstream to downstream ranges in ppm (μg g^?1): As 3,000 to <200, Cd 30 to <0.1, Cu 1,500 to 10, Pb 2,000 to <10, Sb 3000 to <150, and Zn 3,000 to <200. Organic-rich (1.3–2.6% total organic carbon, TOC), sandysilty overbank clay has been analyzed to represent suspended load materials. The high content of heavy metals in the overbank clay throughout the river and estuary systems indicates the importance of suspended sediment transport for dispersing heavy metals from natural erosion and anthropogenic mining activities of the sulfide deposit. The organic-poor (0.21–0.37% TOC) river bed sand has been analyzed to represent bedload transport of naturally-occurring sulfide minerals. The sand has high concentrations of metals upstream but these decrease an order of magnitude in the lower estuary. Although heavy metal contamination of estuary mouth beach sand has been diluted to background levels estuary mud exhibits increased contamination apparently related to finer grain size, higher organic carbon content, precipitation of river-borne dissolved solids, and input of anthropogenic heavy metals from industrial sources. The contaminated estuary mud disperses to the inner shelf mud belt and offshore suspended sediment, which exhibit metal anomalies from natural erosion and mining of upstream Rio Tinto sulphide lode sources (Pb, Cu, Zn) and industrial activities within the estuary (Fe, Cr, Ti). Because heavy metal contamination of Tinto-Odiel river sediment reaches or exceeds the highest levels encountered in other river sediments of Spain and Europe, a detailed analysis of metals in water and suspended sediment throughout the system, and epidemiological analysis of heavy metal effects in humans is appropriate.     

Granite diapirism in the Rum Jungle area,Northern Australia

Early studies in the Rum Jungle area suggested an intrusive relationship between the Rum Jungle and Waterhouse “Granites”, and the overlying sediments. It was later shown that the granitic “intrusions” were Archaean basement complexes onto which Lower Proterozoic sediments had been deposited. Polyphase folding was postulated as being responsible for doming of the basement and cover rocks.This paper proposes to show that the domed structures in the Rum Jungle area, and the emplacement of Middle Proterozoic granites in the Pine Creek Geosyncline were related, and caused by diapiric intrusion of granites, in a solid state, into basement complexes and cover rocks.Structural and metamorphic evidence in support of diapiric intrusion in the Rum Jungle area includes: pebble deformation within steeply dipping beds of quartz conglomerate; disappearance of polyphase fold structures away from the basement complexes; bending of folded country-rock strata into concordance with the complex—sediment contact; and metamorphic and metasomatic alteration of sediments in contact with the basement complexes. Gravity data show mass deficiencies in the Archaean complexes which possibly coincide with young granite diapirs.     

Sediment-water interactions in the metal-contaminated floodplain of the Clark Fork River,Montana, USA

The distribution and concentration of metals and metalloids in the floodplain of the Clark Fork River of western Montana, USA, are mainly controlled by post-depositional diagenetic mechanisms of metal fractionation. Due to the influx of wastes into the river's headwaters from mining processes around the turn of the century, extensive amounts of contaminated material were deposited onto the floodplain. Tailings were deposited as widespread overbank deposits and point bars adjacent to abandoned channels, and are characterized by orange and gray mottled sediment, which is devoid of vegetation and covered by a blue metal sulfate precipitate during dry periods. Examination of stratigraphic profiles of floodplain sediment indicates three periods of deposition: 1) pre-mining, represented by coarse sand and organic overbank deposits under reducing conditions; 2) syn-mining, characterized by transition sediments and tailings deposits under oxidizing conditions; and, 3) post-mining, distinguished by grass-bound topsoil.Sites were established where sediments and water throughout the stratigraphic section were collected and analyzed. Chemical analyses indicate enriched concentrations of cadmium, copper, manganese, and zinc in sediments and porewater, and arsenic in groundwater, in areas contaminated by tailings deposits. Vertical trends in concentrations of metals show that they are distributed based on apportionment of metal phases between reducing-oxidizing environments and pH fluctuations.     

Background levels of potentially toxic metals from soils of the Pisa coastal plain (Tuscany, Italy) as identified from sedimentological criteria

Identification of reliable background values of potentially toxic metals in sediments requires detailed integration of geochemical data with accurate sedimentological studies. Through analysis of 60 soil samples from the Pisa coastal plain, this study shows to what extent sediment provenance and facies characteristics may influence the natural distribution of potentially toxic metals (Cr, Ni, Cu, Zn, Pb) within alluvial and coastal sediments. Metals supplied to the alluvial plain are mostly concentrated within the finest sediment fraction (floodplain clays), while coarser crevasse and overbank deposits exhibit invariably lower metal contents. Beach-ridge sands display the lowest metal concentrations. Transport of ophiolitic detritus by the longshore drift may account for locally high Cr concentrations within beach deposits. Geochemical fingerprinting of individual facies associations in terms of natural metal contents results in the construction of a geologically-based geochemical map. This map offers a more reliable depiction of spatial distribution of background levels than interpolation techniques based uniquely upon statistical methods. Matching background values against metal concentrations from topsoil samples leads to the reliable assessment of the pollution status of Pisa coastal plain. Metal contents exceeding the threshold values designated for contaminated areas (Cr) simply reflect catchment geology, and are not the product of artificial contamination. On the other hand, anthropogenic disturbance may be detected even where metal contents (Pb, Cu) lie below the threshold values. The use of sedimentological criteria is presented here as a pragmatic tool to enhance predictability of natural metal contents in sediments, with obvious positive feedbacks for legislative purposes and environmental protection.     

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.     

Pb isotope evidence for contaminant-metal dispersal in an international river system: The lower Danube catchment,Eastern Europe

Lead isotope signatures (²⁰⁷Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁶Pb, ²⁰⁸Pb/²⁰⁴Pb, ²⁰⁶Pb/²⁰⁴Pb), determined by magnetic sector ICP-MS in river channel sediment, metal ores and mine waste, have been used as geochemical tracers to quantify the delivery and dispersal of sediment-associated metals in the lower Danube River catchment. Due to a diverse geology and range of ore-body ages, Pb isotope signatures in ore-bodies within the lower Danube River catchment show considerable variation, even within individual metallogenic zones. It is also possible to discriminate between the Pb isotopic signatures in mine waste and river sediment within river systems draining individual ore bodies. Lead isotopic data, along with multi-element data; were used to establish the provenance of river sediments and quantify sedimentary contributions to mining-affected tributaries and to the Danube River. Data indicate that mining-affected tributaries in Serbia and Bulgaria contribute up to 30% of the river channel sediment load of the lower Danube River. Quantifying relative sediment contributions from mining-affected tributaries enables spatial patterns in sediment-associated metal and As concentrations to be interpreted in terms of key contaminant sources. Combining geochemical survey data with that regarding the provenance of contaminated sediments can therefore be used to identify foci for remediation and environmental management strategies.     

Heavy metal contamination and their distribution in different size fractions of the surficial sediment of Haihe River, China

Heavy metal contamination and their distribution in different size fractions of the surficial sediment in Haihe River, China have been investigated. These results reveal that the heavy metal contamination of Haihe River is closely related to the contaminating sources along the river and has the order: Cd > Cu > Pb > Cr. The contents of these heavy metals in the sediment of Haihe River are at least two times higher than their background values and the highest contaminating metal, Cd, is 15.5 times higher than its background value and determined in the urban area of Tianjin city. The surficial sediments of Haihe River, with 70% particles smaller than 20 μm, belong to sandy clay containing about 28% clay and 42% silt. Electron micrographs and x-ray analysis show that the concentrations of heavy metals depend on the particle size of sediments. The highest concentrations for most metals exist in fine-grained sediments, which are mainly composed of silicates, oxides, and hydroxides of Si, Fe, and Al. In contrast, lower levels of heavy metals are usually found in the coarse sandy sediments, which are composed of quartz, feldspar, and other rocky substances. Based on the results in the present study of the surficial sediments of Haihe River, the contents of Cr, Cu, Pd, and Cd in finer sediments are 2.4, 3.9, 2.8, and 3.6 times higher than those in coarse sandy sediments, respectively. Obviously, because of rapid industrial development in this area during the last few decades, the surficial sediments of Haihe River, especially those finer fractions, have been seriously contaminated by heavy metals.     

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.     

Historical environmental pollution trend and ecological risk assessment of trace metals in marine sediments off Adyar estuary,Bay of Bengal,India

Geochemical, mineralogical and textural analyses were carried out in core sediments off Adyar estuary, Bay of Bengal, India to record the contamination trend from urban and industrial activities during the historical past. Quartz, feldspar, kaolinite, chlorite and illite were the main lithogenic and clay minerals; carbonate was the predominant biogenic mineral. Trace metals (Fe, Al, Cu, Cr, Ni, Pb and Zn) indicate more enrichment in the surface sediment layers due to recent anthropogenic activities. The mean anthropogenic factor (AF) values for trace metals in core sediments decreased in the following order: Cr > Ni > Zn > Cu > Pb. The pollution load index (PLI) values in Adyar core sediments ranged from 1 to 1.25 with an average of 1.07. Based on AF, PLI, and sediment quality guidelines values for trace metals, significant metal enrichment and ecological risk were obtained in upper-most sediment layer. Multivariate statistical methods such as correlation matrix, principal component analysis and cluster analysis were carried out to find the relationships among the texture size, metals and minerals. The pollution of Adyar estuarine sediments was started in the 1960s, responding to the rapid economic development in Chennai coastal and Adyar estuarine region in the last five decades. Despite these high concentrations in the upper layer, development and expansion of industries are still continuing. The stricter regulations for the discharge and remediation of sediments are urgent for the conservation of environments and human health.     

The geological setting of tourmalinite at Rum Jungle,N.T., Australia — genetic and economic implications

Tourmalinite is a common rock type associated with Proterozoic strata-bound mineral deposits. Although common, it is often difficult to recognise in the field, leading to misidentification. It occurs as a conformable banded quartz-tourmaline lithological unit comprising at least 15% and as much as 50% of the rock. At Rum Jungle, tourmalinite occurs within the oldest sediments (arenites and magnesites) as distinct lenses, as facies equivalents of quartz-magnetite units and mafic schists (tuffs?) and distal equivalents of polymetallic sulfides. Distinct layering, slump folding, rip-up clasts and the association with diagenetic pyrite suggest a sedimentary environment. Enechelon fracturing of the fine-grained, light green tourmaline crystals spectacularly supports pre-deformation formation. The crystals are optically and chemically zoned parallel to the c axis, with irregular growth lamellae width — which supports a pre-regional metamorphic origin. Analyses show the tourmaline to be the Mg-rich variety “dravite”. Most tourmalinites are interpreted as subaqueous marine deposits. It is more likely that they form in lacustrine, shallow water, evaporitic environments, particularly continental rifts. Suitable B-bearing fluids can be generated by hotspring activity and mobilized by CO₂-rich fluids. Association with chemical sediments suggests tourmalinites also have a chemical sediment precursor. Ample evidence at Rum Jungle supports the notion of a continental rift environment, which was the site of deposition of fluvial arenites and alkaline, evaporitic lake sediments. Localised hot-spring activity contributed B-bearing fluids which precipitated chemical sediments according to the pertaining pH, temperature etc. Diagenetic alteration produced the tourmalinite now present. These tourmalinites are comparable to those of similar age elsewhere e.g. Sullivan, Broken Hill. They can be genetically modelled upon Recent borate concentrations, all of which occur in continental rift environments.     

Zn, Pb, Cu and As distribution patterns in overbank and medium-order stream sediment samples: their use in exploration and environmental geochemistry

Overbank and medium-order stream sediment samples were collected in Belgium and Luxembourg from 66 sampling locations (area of about 33,000 km²) and analysed for major and trace elements among which Zn, Pb, Cu and As. At each sampling location large bulk samples were taken, namely in the lower (normally at ≥1.5 m depth, over an interval of about 20–40 cm) and upper (normally upper 5–25 cm) parts of the overbank profiles and from the stream sediments. Furthermore, at a number of these sites, a detailed geochemical analysis of vertical overbank sediment profiles (sampling intervals of 10–20 cm) was subsequently carried out to unravel element variations through time and to help in the overall evaluation. For most sampled sections evidences such as ¹⁴C-dating and the absence of anthropogenic particles point towards a pre-industrial and often pristine origin of the lower overbank sediment samples. From the latter bulk samples, mean background concentrations were deduced. They reveal the existence of significant differences between the northern and southern part of Belgium (incl. Luxembourg) which relate to the difference in geological substrate. In the north dominantly non-lithified Quaternary and Tertiary sands, marls and clays occur while in the south Palaeozoic sandstones, shales and carbonate rocks outcrop. Consequently separate mean background values were calculated for the two areas. In the southern study area, some anomalous metal concentrations have been recorded in pre-industrial sediments. They are derived from mineralised Palaeozoic rocks, a feature which could be of interest for base metal exploration. In the upper overbank and stream sediments, in general, higher heavy metal and As contents were recorded with highest values in areas with metal mining, metal melting and cokes treatment industries. By comparing the trace element concentrations of the upper overbank or stream sediment samples with the concentrations detected in the lower overbank samples at each of the sampling locations, and by evaluating the vertical distribution patterns where available, the degree of pollution of the alluvial plain and the present-day stream sediments can be assessed. From this exercise, it is clear that highest pollution occurs in the northern part of Belgium, which relates to its high population density and industrial development.     

Mobility of heavy metals as a function of pH of samples from an overbank sediment profile contaminated by mining activities

Parts of the flood plains north of the Harz Mountains are contaminated with heavy metals, such as Pb, Cu, Zn and Cd derived from mining, which has been carried out in the Harz Mts. since the Middle Ages. It is important to know the mobility of the heavy metals in these overbank sediments in order to estimate the danger to the environment arising from this source. This paper deals with the effect of pH on heavy-metal mobility, using a constant-pH method. The investigations were carried out on an overbank sediment profile near Salzgitter Bad, north of the Harz Mts. The mobility of the heavy metals in the overbank sediment profile is described as a function of pH and depth. Besides the mobile heavy-metal fraction at a certain pH, the buffering capacity of the sediment at this pH must be taken into consideration. The different layers of the overbank sediment profile show distinct differences in buffering capacity and a natural pH harrier could be identified in the upper part of the profile. Therefore, to avoid increasing heavy-metal mobility the natural layering of the overbank sediment profile should not be disturbed. Two different kinds of desorption experiments at constant pH are also discussed, as well as the conversion of the heavy-metal species in the ore minerals into the species in the sediment.     

River system recovery following the Novaţ-Roşu tailings dam failure, Maramureş County, Romania

The River Vişeu catchment in Maramureş County, northwestern Romania, has a long history of base and precious metal mining. Between 1994 and 2003 waste from mining activity at Baia Borşa was stored in the Novaţ-Roşu tailings pond in the upper Vişeu catchment. However, in March 2000, the tailings dam failed releasing approximately 100,000 m³ of contaminated water and 20,000 t of mineral-rich solid waste, which was routed downstream through the Rivers Novaţ, Vaser and Vişeu into the River Tisa. Following the accident metal (Cd, Cu, Pb, Zn) concentrations in river water and river channel sediment were assessed in samples collected annually (July 2000, 2001, 2002 and 2003) from 29 sites in the Vişeu catchment, downstream of the tailings pond. Additionally, the speciation of sediment-associated metals was established using a 4-stage sequential extraction procedure (SEP) and Pb isotope analysis (^206/204Pb and ^207/204Pb) was carried out to establish the provenance of contaminated sediments. Metal concentrations in river water were found to comply with EU directive ‘target’ values within four months of the failure. However, the impact of the spill upon river channel sediments was found to be much longer-lasting, with evidence of the delayed downstream remobilization of tailings stored within the narrow Novaţ valley following the dam failure, as well as continued inputs of contaminated sediment to the River Vişeu from the River Tisla, another mining-affected tributary. Comparison with data from other recent tailings dam failures, indicates that river system recovery rates depend upon local geomorphological conditions, hydrological regimes, and the nature and scale of post-spill clean-up operations.     

Heavy metal trends in the Calabar River, Nigeria

. Heavy metal concentrations in sediments of the Calabar River: Pb (0.6–30 ppm); Ni (1.2–22.5 ppm); Cr (0.6–3.3 ppm); Cu (0.3–48 ppm); Zn (0.8–27 ppm); Fe (0.2–2,880 ppm) and V (0 ppm) are generally below levels that are known to be harmful to aquatic biota. Metal levels displayed marked seasonal, spatial and tidal variations, which are attributed to both anthropogenic influences and natural processes in the environment. Iron and Cr increased during the dry season (January), while Cu, Zn, Pb and Ni had their peak values in the wet season (September). High values of metals during the wet season indicate inputs through human activities mediated by rainfall. Relatively higher concentrations of metals are obtained during high tide compared to low tide regime. This is attributed to redox processes in the sediment and subsequent displacement of sediment pore water rich in metals by seawater intrusion during high tide. Higher values of Fe observed in the dry compared to the wet season may be attributed to oxidation and precipitation of soluble forms brought into the river during the wet season.     

Bed sediment-associated trace metals in an urban stream, Oahu, Hawaii

 Of the 117 stream and lake systems sampled nationwide, fish from Manoa Stream on Oahu, Hawaii, have consistently shown the highest Pb concentrations. Therefore a detailed study was conducted to examine total metal contents in bed sediments from a 5.8-km stretch of Manoa Stream. A total of 123 samples (<63 μm) were examined for 18 elements and 14 samples for 21 elements. Selected samples were also examined using different leach solutions to examine metal phase associations. All trace metal data, computations of enrichment ratios and the modified index of geoaccumulation point to mineralogical control for Cr and Ni; minor anthropogenic contamination for Ba, Cd, Cu, Hg and Zn; and a very strong contamination signal for Pb. Maximum Pb contents (up to 1080 mg kg⁻¹) were associated with anthropogenic material dumping in minor tributaries, storm sewer sediments and sediments in the “lower” section of the basin. Proportionally Pb had the highest non-residual component of elements examined; dominantly in the reducible phase associated with Mn and amorphous Fe oxyhydroxides. The contamination signal was typically lowest in the “undisturbed” headwater reach of the basin (above 5.1 km) with significant increases throughout the “residential” and “commercial-institutional” zones of the mid-basin. The spatial pattern of bed sediment contamination and evidence from storm sewer-outlet sediments strongly indicates that Pb, and to a lesser degree some other metals, is still being transported to the stream and the primary agent is soil erosion and transport of metals sorbed to sediments. The primary source of sediment-associated metals is considered to be the automobile, though other minor sources can not be ruled out. Received: 3 November 1998 · Accepted: 26 January 1999     

Studies on the variations of heavy metals in the marine sediments off Kalpakkam,East Coast of India

During the last two decades, the coastal environment of southeast India has experienced intense developments in industry, urbanization and aquaculture. Moreover, the 2004 mega tsunami has devastated this coast, thus affecting the coastal sediment characteristics. These two phenomena prompted a study to characterize the sediment, to understand the mechanisms influencing the distribution of heavy metals and to create baseline data for future impact assessment. Results showed that the coastal sediment was carpeted with a mosaic of sand and silty sand with a minor amount of clay. Heavy metal values showed maximum variation for Fe and minimum for Cd. Their average values showed the following decreasing trend: Fe > Cu > Zn > Pb > Cr > Ni > Cd. This study shows that the major source of metals at Kalpakkam coast are land-based anthropogenic ones, such as, discharge from industrial waste, agricultural waste, urban, municipal and slum sewage into the Buckingham canal, which in turn discharges into the sea through backwaters, particularly during northeast monsoon period. A clear signature of the role of backwater discharge increasing the concentration of a few metals in the coastal sediments during monsoon period was observed. Assessments of the degree of pollution, concentration factor (CF), geoaccumulation index (I _geo) and pollution load index (PLI) have been calculated. CF values and I _geo indicated that the coastal sediment is moderately polluted by Cu and Cd. Increase in Cu, Pb and Zn concentration during the monsoon period (October–January) compared to the rest of the year was noticed. Factor analysis and correlation among the heavy metals concluded that Cr, Ni, Cd and Fe are of crustal origin, whereas, Cu, Pb and Zn are from anthropogenic sources. Organic carbon content in the sediment increased during monsoon period, pointing to the role of land runoff and backwater discharge in enhancing its content. The study also elucidates the impact of the recent tsunami in depleting metal content in the coastal sediment as compared to the pre-tsunami period.     

Storage of sediment-associated nutrients and contaminants in river channel and floodplain systems

Samples of fine-grained channel bed sediment and overbank floodplain deposits were collected along the main channels of the Rivers Aire (and its main tributary, the River Calder) and Swale, in Yorkshire, UK, in order to investigate downstream changes in the storage and deposition of heavy metals (Cr, Cu, Pb, Zn), total P and the sum of selected PCB congeners, and to estimate the total storage of these contaminants within the main channels and floodplains of these river systems. Downstream trends in the contaminant content of the <63 μm fraction of channel bed and floodplain sediment in the study rivers are controlled mainly by the location of the main sources of the contaminants, which varies between rivers. In the Rivers Aire and Calder, the contaminant content of the <63 μm fraction of channel bed and floodplain sediment generally increases in a downstream direction, reflecting the location of the main urban and industrialized areas in the middle and lower parts of the basin. In the River Swale, the concentrations of most of the contaminants examined are approximately constant along the length of the river, due to the relatively unpolluted nature of this river. However, the Pb and Zn content of fine channel bed sediment decreases downstream, due to the location of historic metal mines in the headwaters of this river, and the effect of downstream dilution with uncontaminated sediment. The magnitude and spatial variation of contaminant storage and deposition on channel beds and floodplains are also controlled by the amount of <63 μm sediment stored on the channel bed and deposited on the floodplain during overbank events. Consequently, contaminant deposition and storage are strongly influenced by the surface area of the floodplain and channel bed. Contaminant storage on the channel beds of the study rivers is, therefore, generally greatest in the middle and lower reaches of the rivers, since channel width increases downstream. Comparisons of the estimates of total storage of specific contaminants on the channel beds of the main channel systems of the study rivers with the annual contaminant flux at the catchment outlets indicate that channel storage represents <3% of the outlet flux and is, therefore, of limited importance in regulating that flux. Similar comparisons between the annual deposition flux of specific contaminants to the floodplains of the study rivers and the annual contaminant flux at the catchment outlet, emphasise the potential importance of floodplain deposition as a conveyance loss. In the case of the River Aire the floodplain deposition flux is equivalent to between ca. 2% (PCBs) and 36% (Pb) of the outlet flux. With the exception of PCBs, for which the value is ≌0, the equivalent values for the River Swale range between 18% (P) and 95% (Pb). The study emphasises that knowledge of the fine-grained sediment delivery system operating in a river basin is an essential prerequisite for understanding the transport and storage of sediment-associated contaminants in river systems and that conveyance losses associated with floodplain deposition exert an important control on downstream contaminant fluxes and the fate of such contaminants.     

High spatial resolution sampling of metals in the sediment and water column in Port Jefferson Harbor, New York

Eighteen sediment samples and six water-column samples were collected in a small (6 km²), coastal embayment (Port Jefferson Harbor, New York) to define a high-resolution spatial distribution of metals and to elucidate sources of contaminants to the harbor. Sediment metal (Ag, Cu, Fe, Ni, Pb, V, and Zn) concentrations varied widely, reflecting differences in sediment grain size, with higher metal concentrations located in the fine-grained inner harbor sediments. Calculated enrichment factors for these sediments show that Ag, Pb, Cu, and Zn are elevated relative to both crustal abundances and their respective abundances in sediments in central Long Island Sound. Metal concentrations were 1.2 to 10 fold greater in water from the inner harbor compared to water from Long Island Sound collected outside the mouth of the harbor. Spatial variations in trace metals in surface waters within the bay parallel the spatial variations of trace metals in sediments within the harbor. Elevated water-column metal concentrations appear to be partially derived from a combination of diagenetic remobilization from contaminated sediments (e.g., Ag) and anthropogenic sources (e.g., Cu and Zn) within the southern portions of the harbor. Although the National Status and Trends Program had reported previously that sediment metal concentrations in Port Jefferson Harbor were low, the results of this study show sediment metals have high spatial variability and are enriched in the inner harbor sediments at levels comparable to more urbanized western north shore Long Island harbors.     

Iron reduction in the sediments of a hydrocarbon-contaminated aquifer

Sediments sampled at a hydrocarbon-contaminated, glacial-outwash, sandy aquifer near Bemidji, Minnesota, were analyzed for sediment-associated Fe with several techniques. Extraction with 0.5 M HCl dissolved poorly crystalline Fe oxides and small amounts of Fe in crystalline Fe oxides, and extracted Fe from phyllosilicates. Use of Ti-citrate-EDTA-bicarbonate results in more complete removal of crystalline Fe oxides. The average HCl-extractable Fe(III) concentration in the sediments closest to the crude-oil contamination (16.2 μmol/g) has been reduced by up to 30% from background values (23.8 μmol/g) as a result of Fe(III) reduction in contaminated anoxic groundwater. Iron(II) concentrations are elevated in sediments within an anoxic plume in the aquifer. Iron(II) values under the oil body (19.2 μmol/g) are as much as 4 times those in the background sediments (4.6 μmol/g), indicating incorporation of reduced Fe in the contaminated sediments. A 70% increase in total extractable Fe at the anoxic/oxic transition zone indicates reoxidation and precipitation of Fe mobilized from sediment in the anoxic plume. Scanning electron microscopy detected authigenic ferroan calcite in the anoxic sediments and confirmed abundant Fe(III) oxyhydroxides at the anoxic/oxic boundary. The redox biogeochemistry of Fe in this system is coupled to contaminant degradation and is important in predicting processes of hydrocarbon degradation.     

Channel processes as a factor controlling accumulation of heavy metals in river bottom sediments: consequences for pollution monitoring (Upper Silesia, Poland)

 An evaluation of the influence of channel processes (erosion, accumulation, processing of channel sediments) on the dispersal of heavy metals in bottom sediments was carried out in the channels of the Sztoła and Biała Przemsza rivers in Upper Silesia, Poland. These rivers receive waters from a Zn and Pb mine. Mine waters transport a large amount of fine-grained sediments contaminated with heavy metals. The polluted material is accumulated in these stream courses and mixed with nearly homogeneous sandy sediment derived from erosion of the river banks and bed. Because these alluvia are easily set in motion, the distribution of heavy metal concentration in the channel in fraction <1 mm reflects differences in physical processes of sedimentation in its cross-section. The minimal values in active channel and maximal in the near-bank zone are typical for those channel sections where heavy metals, present in a solid state, are transported as a suspended load (normally the largest part of a polluted river course). In short sections heavy metals associated with the grains of a large mass which has accumulated in the active channel are transported as a bed load and the typical distribution pattern is reversed (in fractions both <1 mm and <0.063 mm). Such regularities can be disturbed in localities where strong, turbulent flow or frequent eddying occur and Mn oxides and hydrooxides and associated elements precipitate. The smallest variation in heavy metal concentration in the homogenous, fine-grained bank sediments which are trapped by plants below water level is a feature which recommends these localities as being the most suitable for monitoring of river pollution. Received: 11 November 1997 · Accepted: 12 March 1998