A statistical assessment of the form of trace metals in oxidized estuarine sediments employing chemical extractants

The thin layer of oxidized sediment at the sediment—water interface plays an important role in the chemical and biological interactions of trace metals in estuaries. Chemical extractants can be useful in defining trace metal interactions in sediments. Extractions may aid in determining the abundance of the operationally-defined forms of substrates which are the most active in binding metals in sediments; in operationally-defining an “extractable” phase of trace metals in sediments; and in providing information necessary for determining the bioavailability of sediment-bound metals. Comparison of 10 techniques for metal and substrate extractions among the sediments of 19 estuaries from south and west England indicate substrate characterization is best accomplished by Fe and Mn extractions with acid ammonium oxalate or 1N HCl, and humic substances extraction with 0.1N NaOH or 1N ammonia. Partial fractionation of trace metals is best accomplished with 1N HCl. Statistical relationships indicate the extractable phase of Fe is more important than total Fe in binding Ag, Cd, Cu, Pb and Zn in oxidized sediments, and the operationally-defined humic substance fraction of organic materials is highly important in binding Ag and Cu. Statistical analysis within specific subsets of data indicate trace metals are partitioned among several substrates in most sediments, the substrates compete with one another for the metals, and the outcome of the competition is strongly influenced by the concentrations of the different substrates in the sediment.     

DYNAMICS OF SEDIMENT-ASSOCIATED METALS IN A HIGHLY URBANISED CATCHMENT: BRADFORD, WEST YORKSHIRE

Urban watercourses are potential hazards because of their rapid flow changes, poor water quality and contaminated sediments. This study is a preliminary field investigation into fine sediment-associated metal contamination and its transport dynamics in a highly urbanised catchment in West Yorkshire, UK. Spatial and temporal changes in the concentration of channel-bed sediment-associated metals are investigated, and the fluxes of selected suspended sediment-associated metals, during an extreme high flow event, are determined. Channel-bed sediments were more contaminated at the most heavily urbanised sites. Data suggest that contaminated bed sediments could accumulate and possibly become increasingly contaminated between high-flow events, prior to being flushed from the system. Fluxes of contaminated suspended sediments were very high at the peak of the high flow event. The spatial and temporal dynamics of contaminated fine sediment which were identified in this study could inform planners with regard to future monitoring strategies.     

Seasonal nutrient dynamics in a chalk stream: the River Frome, Dorset, UK

Chalk streams provide unique, environmentally important habitats, but are particularly susceptible to human activities, such as water abstraction, fish farming and intensive agricultural activity on their fertile flood-meadows, resulting in increased nutrient concentrations. Weekly phosphorus, nitrate, dissolved silicon, chloride and flow measurements were made at nine sites along a 32 km stretch of the River Frome and its tributaries, over a 15 month period. The stretch was divided into two sections (termed the middle and lower reach) and mass balances were calculated for each determinand by totalling the inputs from upstream, tributaries, sewage treatment works and an estimate of groundwater input, and subtracting this from the load exported from each reach. Phosphorus and nitrate were retained within the river channel during the summer months, due to bioaccumulation into river biota and adsorption of phosphorus to bed sediments. During the autumn to spring periods, there was a net export, attributed to increased diffuse inputs from the catchment during storms, decomposition of channel biomass and remobilisation of phosphorus from the bed sediment. This seasonality of retention and remobilisation was higher in the lower reach than the middle reach, which was attributed to downstream changes in land use and fine sediment availability. Silicon showed much less seasonality, but did have periods of rapid retention in spring, due to diatom uptake within the river channel, and a subsequent release from the bed sediments during storm events. Chloride did not produce a seasonal pattern, indicating that the observed phosphorus and nitrate seasonality was a product of annual variation in diffuse inputs and internal riverine processes, rather than an artefact of sampling, flow gauging and analytical errors.     

Impacts of runoff from sulfuric soils on sediment chemistry in an estuarine lake

The impact of runoff from sulfuric soils in the heavily drained Cudgen Lake floodplain, eastern Australia on water quality and downstream coastal lake sediments has been examined. The oxidation of sulfidic soils and the transformation into sulfuric soils leads to changes not only in the upper soil profile but also affects drainage water quality and the chemistry of bottom sediments in receiving waters. Oxidation transforms the soil from a sink for sulfur and metals to a significant source for downstream environments. Sulfuric soils within the Cudgen Lake catchment contain 9.18 x 10(5) mol H+ per hectare as well as elevated concentration of metals (e.g. Al, Fe, Mn) and sulfate. These products of sulfidic soil oxidation are transported efficiently from the soil profile by the constructed drainage network and into the downstream lake system. The acid volatile sulfur (AVS), chromium reducible sulfur (CRS), total sulfur, organic carbon, and reactive iron contents present in the solid phase of the lake sediments are reported. The AVS/CRS, DOP and DOS values observed in the lake sediments show that natural monosulfide formation in the near surface sediments has been enhanced due to increased inputs of organic matter, sulfate, ferrous iron and other metals following development of the catchment. There are elevated concentrations of metals (e.g. As, Al, Cd, Cr, Hg, Zn and Pb) in the upper layer of monosulfidic lake sediments compared with the underlying pyritic sediments some of which exceed sediment quality guidelines. These metals could be released by dredging or through re-suspension during high flow conditions or enter the food chain.     

Modelling sediment-microbial dynamics in the South Nation River, Ontario, Canada: Towards the prediction of aquatic and human health risk

Runoff from agricultural watersheds can carry a number of agricultural pollutants and pathogens; often associated with the sediment fraction. Deposition of this sediment can impact water quality and the ecology of the river, and the re-suspension of such sediment can become sources of contamination for reaches downstream. In this paper a modelling framework to predict sediment and associated microbial erosion, transport and deposition is proposed for the South Nation River, Ontario, Canada. The modelling framework is based on empirical relationships (deposition and re-suspension fluxes), derived from laboratory experiments in a rotating circular flume using sediment collected from the river bed. The bed shear stress governing the deposition and re-suspension processes in the stream was predicted using a one dimensional mobile boundary flow model called MOBED. Counts of live bacteria associated with the suspended and bed sediments were used in conjunction with measured suspended sediment concentration at an upstream section to allow for the estimation of sediment associated microbial erosion, transport and deposition within the modelled river reach. Results suggest that the South Nation River is dominated by deposition periods with erosion only occurring at flows above approximately 250 m³ s⁻¹ (above this threshold, all sediment (suspended and eroded) with associated bacteria are transported through the modelled reach). As microbes are often associated with sediments, and can survive for extended periods of time, the river bed is shown to be a possible source of pathogenic organisms for erosion and transport downstream during large storm events. It is clear that, shear levels, bacteria concentrations and suspended sediment are interrelated requiring that these parameters be studied together in order to understand aquatic microbial dynamics. It is important that any management strategies and operational assessments for the protection of human and aquatic health incorporate the sediment compartments (suspended and bed sediment) and the energy dynamics within the system in order to better predict the concentration of indicator organism.     

A novel tracer technique for the assessment of fine sediment dynamics in urban water management systems

Urban storm water run off can reduce the quality of receiving waters due to high sediment load and associated sediment-bound contaminants. Consequently, urban water management systems, such as detention ponds, that both modify water quantity through storage and improve water quality through sediment retention are frequently-used best management practices. To manage such systems effectively and to improve their efficiency, there is a need to understand the dynamics (transport and settling) of sediment, and in particular the fine sediment fraction (<63 μm) and its associated contaminants within urban storm water management systems. This can be difficult to achieve, as modelling the transport behaviour of fine-grained and cohesive sediment is problematic and field-based measurements can be costly, time-consuming and unrepresentative.The aim of this study was to test the application of a novel cohesive sediment tracer and to determine fine sediment transport dynamics within a storm water detention pond. The cohesive sediment tracer used was a holmium labelled montmorillonite clay which flocculated and had similar size and settling velocity to the natural pond sediment it was intended to mimic. The tracer demonstrated that fine sediment was deposited across the entire pond, with the presence of reed beds and water depth being important factors for maximising sediment retention. The results of the sediment tracer experiment were in good agreement with those of a mathematical sediment transport model. Here, the deposited sediment tracer was sampled by collecting and analysing surface pond sediments for holmium. However, analysis and sampling of the three dimensional suspended tracer ‘cloud’ may provide more accurate information regarding internal pond sediment dynamics.     

The phosphorus content of fluvial sediment in rural and industrialized river basins

The phosphorus content of fluvial sediment (suspended sediment and the < 63 microm fraction of floodplain and channel bed sediment) has been examined in contrasting rural (moorland and agricultural) and industrialized catchments in Yorkshire, UK. The River Swale drains a rural catchment with no major urban and industrial areas, and the total phosphorus (TP) content of fluvial sediment is generally within the range 500-1,500 microg g(-1). There is little evidence of any major downstream increase in TP content. In contrast, fluvial sediment from the industrialized catchments of the Rivers Aire and Calder exhibits both higher levels of TP content and marked downstream increases, with values of TP content ranging from < 2,000 microg g(-1) in headwater areas upstream of the main urban and industrial areas, to values > 7,000 microg g(-1) at downstream sites. These elevated levels reflect P inputs from point sources, such as sewage treatment works (STWs) and combined sewer overflows. The influence of STWs is further demonstrated by the downstream increase in the inorganic P/organic P ratio from < 2 in the headwaters to > 4 in the lower reaches. Comparison of the P content of suspended sediment with that of the <63 microm fraction of potential source materials suggests that topsoil from upland moorland/pasture and from cultivated areas, and channel bank material are likely to be the main sources of particulate P (PP) in the River Swale and in the headwaters of the Rivers Aire and Calder. In the middle and lower reaches of the Rivers Aire and Calder, inputs associated with urban and industrial land uses, such as STWs, industrial effluents and street dust, are likely to represent the dominant sources of PP. During high flow events, such urban inputs may be diluted by inputs from moorland and agricultural land in the headwaters. Consequently, for all three rivers, there are inverse relationships between the TP content of suspended sediment and both discharge and suspended sediment concentration, reflecting changes in sediment and P sources during high flow events. Spatial variations in the P contents of the < 63 microm fraction of overbank floodplain deposits and channel bed sediment evidence a similar pattern as those for suspended sediment, with relatively low levels of TP in the River Swale and elevated levels in the middle and downstream reaches of the Rivers Aire and Calder. The PP concentrations associated with floodplain and channel bed sediment are, however, lower than equivalent values for suspended sediment, and this primarily reflects the differences in the particle size composition between the three types of sediments. Rates of floodplain deposition and the amounts of fine-grained sediment stored in the river channels are relatively high, and suggest that such environments may represent important sinks for PP. Based on the sediment samples collected from the study basins, a simple four-fold classification which relates the TP content of suspended sediment to upstream land use has been established. Both the range and the absolute values of TP content tend to increase with an increase in the level of urbanization and industrialization.     

Cu, Pb and Zn contamination in Nuuanu watershed, Oahu, Hawaii

Trace metal contamination in urban aquatic ecosystems in Hawaii is a significant problem, especially in terms of Cu, Pb, and Zn. These trace metals are linked to automobile usage. An in-depth study was designed to determine the influence of road sediments and storm sewers on bioavailable (0.5 M HCl) trace metal concentrations in bed sediments of Nuuanu stream, Oahu. Lead was the most enriched trace metal in the watershed. Compared to baseline Pb concentrations of <3 mg/kg, road sediments averaged 186 mg/kg, with a maximum value of 3140 mg/kg. Stream bed sediments had average Pb values of 122 mg/kg, with a maximum of 323 mg/kg. Al-normalized enrichment ratios (ERs) for the <63 microm fraction indicated that the watershed was significantly polluted in the lower, urbanized reaches, with maximum ER values of 560 and 94 for Pb in road sediments and stream sediments, respectively. Median ER values for Cu, Pb, and Zn in stream sediments were 2, 36, and 5, respectively. Rainfall events prior to sediment sampling masked any influence that storm sewer outlets might have had on the localized spatial distribution of metals associated with bed sediments. However, there was a general pattern of increasing trace metal concentrations downstream as the fluvial network traversed residential areas and commercial, highly trafficked areas in the lower portions of the watershed.     

Lead,iron, chromium and zinc in road runoff at Pullman,Washington

The inputs of iron, lead, chromium and zinc to a 0.6 acre road surface were investigated. The selection of a viaduct in Pullman, Washington as a study area permitted the exclusion of metal input from non-road surfaces. Dust and precipitation metal deposition rates were measured at the viaduct as well as at a control location. It was found that the primary source of metals at the road surface was the operation of motor vehicles. For three separate storm events, runoff samples were collected, flow was measured and runoff samples were analyzed for total solids, total metals and dissolved-colloidal metals. Less than 5 percent of each metal in the runoff samples existed in the dissolved-colloidal fraction. Mean concentrations of total metals in road runoff were 1.86, 89, 0.139 and 19.1 mg/l for Pb, Fe, Cr, and Zn, respectively. A mathematical model was developed allowing the estimation of metal loadings for a storm event typical of the area, given the total runoff volume for the particular storm event. It was also found that a residual amount of metals remains on the road surface after each storm.     

Sewage-effluent phosphorus: a greater risk to river eutrophication than agricultural phosphorus?

Phosphorus (P) concentrations from water quality monitoring at 54 UK river sites across seven major lowland catchment systems are examined in relation to eutrophication risk and to the relative importance of point and diffuse sources. The over-riding evidence indicates that point (effluent) rather than diffuse (agricultural) sources of phosphorus provide the most significant risk for river eutrophication, even in rural areas with high agricultural phosphorus losses. Traditionally, the relative importance of point and diffuse sources has been assessed from annual P flux budgets, which are often dominated by diffuse inputs in storm runoff from intensively managed agricultural land. However, the ecological risk associated with nuisance algal growth in rivers is largely linked to soluble reactive phosphorus (SRP) concentrations during times of ecological sensitivity (spring/summer low-flow periods), when biological activity is at its highest. The relationships between SRP and total phosphorus (TP; total dissolved P+suspended particulate P) concentrations within UK rivers are evaluated in relation to flow and boron (B; a tracer of sewage effluent). SRP is the dominant P fraction (average 67% of TP) in all of the rivers monitored, with higher percentages at low flows. In most of the rivers the highest SRP concentrations occur under low-flow conditions and SRP concentrations are diluted as flows increase, which is indicative of point, rather than diffuse, sources. Strong positive correlations between SRP and B (also TP and B) across all the 54 river monitoring sites also confirm the primary importance of point source controls of phosphorus concentrations in these rivers, particularly during spring and summer low flows, which are times of greatest eutrophication risk. Particulate phosphorus (PP) may form a significant proportion of the phosphorus load to rivers, particularly during winter storm events, but this is of questionable relevance for river eutrophication. Although some of the agriculturally derived PP is retained as sediment on the river bed, in most cases this bed sediment showed potential for removal of SRP from the overlying river water during spring and summer low flows. Thus, bed sediments may well be helping to reduce SRP concentrations within the river at times of eutrophication risk. These findings have important implications for targeting environmental management controls for phosphorus more efficiently, in relation to the European Union Water Framework Directive requirements to maintain/improve the ecological quality of impacted lowland rivers. For the UK rivers examined here, our results demonstrate that an important starting point for reducing phosphorus concentrations to the levels approaching those required for ecological improvement, is to obtain better control over point source inputs, particularly small point sources discharging to ecologically sensitive rural/agricultural tributaries.     

Production and transport of urban wet weather pollution in combined sewer systems: the “Marais” experimental urban catchment in Paris

An experimental catchment area was set up in the centre of Paris (France) so as to follow up the quality of wet weather flows from the entry to the exit of a combined sewer network. The distinctive characteristic of this site is its location in a town centre and the extent of the equipment used to monitor the water pollution over the whole length of its course through the catchment area. The results obtained show a change in quality between the runoff entering the sewer network and the combined storm water flow at the sewer's outlet, which cannot be explained only by the mixture with domestic wastewater. In particular, an increase was observed in the concentrations of suspended solids (SS), VSS, COD, BOD and Cu, in the proportion of pollutants linked to particles and in the characteristics of the particles. A calculation of the total masses going in and out of the sewer network during a rainfall event shows that the erosion of in-sewer pollution stocks is the main source of particles and of organic matter in wet weather flows, whereas heavy metals loads originated from roof runoff, due to the corrosion of metallic roofs. Particles eroded from the sewer sediments during rain events were found to be quite different from the particles of type A deposits and organic biofilms. Nevertheless, they have mean organic and metallic loads that are of the same order of magnitude as the particles of the organic layer at water sediment interface. A change in the chemical form of heavy metals was noticed during the transport in the sewer and it is suspected that a fraction of the dissolved metals from the runoff is adsorbed on sewer sediments.     

Potential effects of forest fire and storm flow on total mercury and methylmercury in sediments of an arid-lands reservoir

A study was conducted from July 1995 to June 1996 to examine the spatial and temporal changes of mercury concentrations in sediments of an arid-lands reservoir. Prior to the first sample collection in July, a forest fire burned 2930 ha of mixed conifer and ponderosa pine in the watershed of Caballo Reservoir in south-central New Mexico. The fire was eventually extinguished by summer rains and storm runoff resulting in the mobilization and transport of charred vegetative material into an intermittent tributary (Palomas Creek) that drains the watershed into Caballo Reservoir. Concentrations of total mercury (THg), monomethlymercury (MMHg), and total organic carbon (TOC) in surficial sediments revealed fire, followed by storm runoff, enhanced the transport of mercury and organic matter to the reservoir. Concentrations of THg in sediments increased from 7.5 etag/g in July to 46.1 etag/g by November 1995 at one site (Palomas) nearest the outflow of Palomas Creek. No other spatial or temporal trends were observed for THg at other sites throughout the remainder of the study. Concentrations of MMHg in sediments at the Palomas site increased from 0.428 etag/g in July to 12.46 etag/g by October 1995 compared to concentrations in sediments at the remaining sites which ranged from 0.11 to 1.50 etag/g throughout the study. The ratio of MMHg to THg (a gross index of methylation activity) was greatest in sediments from the Palomas site (5.4-33.8%) compared to the remaining sites (0.01-3.60%). The ratio was mirrored by elevated TOC in sediments at the Palomas site (2.5-11.8%) that remained elevated throughout the study. Fire and subsequent late-summer rains may have had a twofold effect on mercury concentrations in Caballo Reservoir. The storm-driven runoff following the forest fire carried mercury complexed to organic matter which resulted in elevated levels of mercury as well as providing a carbon source for microbial methylation processes in sediment.     

The stability of marine sediments at a tidal basin in San Francisco Bay amended with activated carbon for sequestration of organic contaminants

Recent laboratory studies show that adding activated carbon to marine sediments reduces the bioavailability of persistent organic contaminants, such as polychlorinated biphenyls, to benthic organisms. The present work investigates how mixing activated carbon into cohesive sediment affects the stability of sediment obtained from the intertidal zone at the Hunters Point Naval Shipyard Superfund site in South Basin, San Francisco Bay, CA. Our results show for these sediments that mixing activated carbon into sediment does not significantly affect stability of surface sediments, as measured by sediment erosion rate and critical shear stress for incipient motion, thus supporting the potential field application of this technique for in situ stabilization of persistent organic contaminants. Hydrodynamic modeling was used to estimate the maximum bottom shear stress encountered during high-wind storm events at the estuarine inlet from which the sediments were obtained. Comparison of estimated bottom shear stresses with measured critical shear stresses shows that surface sediments will not erode under normal, non-storm conditions. Bottom shear stresses caused by large waves under infrequent high-wind storm conditions may erode surface sediments for short periods of time. We conclude from sediment stability tests and hydrodynamic modeling that mixing activated carbon amendment with cohesive sediment at selected locations within South Basin will not reduce surface sediment stability nor result in significant erosion of treated sediments.     

Contaminants in sediments: remobilisation and demobilisation

In this study, the contaminated anoxic sediment of the Mulde reservoir (Saxony, Germany) was investigated. Several sediment cores were analysed for heavy metals and organic chemicals such as chlorobenzenes and DDTs. The comparison between anoxic and oxidised sediment cores showed the potential danger for heavy metal (Zn and Cd) remobilisation from sediment due to bioturbation or resuspension by flooding. Chemical sequential extraction was used to describe partitioning of heavy metals among different mineralogical components in the sediments. Results showed remobilisation of Zn and Cd from the sediments. The stable fraction (organic/sulfidic-bound) of Zn and Cd decreased from 10 to 3%, and from 35 to 5%, respectively. Simultaneously, the carbonate fraction increased from 3 to 12% for Cd and from 10 to 22% for Zn. Furthermore, the simulation of the diffusion of organic pollutants showed remobilisation of 1,4-dichlorobenzene. The results confirmed the necessity of sediment remediation in the reservoir. Capping seems to be a promising approach for a low-cost remediation.     

Modern and historical fluxes of halogenated organic contaminants to a lake in the Canadian arctic, as determined from annually laminated sediment cores

Two annually laminated cores collected from Lake DV09 on Devon Island in May 1999 were dated using 210Pb and 137Cs, and analyzed for a variety of halogenated organic contaminants (HOCs), including polychlorinated biphenyls (PCBs), organochlorine pesticides, short-chain polychlorinated n-alkanes (sPCAs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and polybrominated diphenyl ethers (PBDEs). Dry weight HOC concentrations in Lake DV09 sediments were generally similar to other remote Arctic lakes. Maximum HOC fluxes often agreed well with production maxima, although many compound groups exhibited maxima at or near the sediment surface, much later than peak production. The lower than expected HOC concentrations in older sediment slices may be due to anaerobic degradation and possibly to dilution resulting from a temporary increase in sedimentation rate observed between the mid-1960s and 1970s. Indeed, temporal trends were more readily apparent for those compound classes when anaerobic metabolites were also analyzed, such as for DDT and toxaphene. However, it is postulated here for the first time that the maximum or increasing HOC surface fluxes observed for many of the major compound classes in DV09 sediments may be influenced by climate variation and the resulting increase in algal primary productivity which could drive an increasing rate of HOC scavenging from the water column. Both the fraction (F(TC)) and enantiomer fraction (EF) of trans-chlordane (TC) decreased significantly between 1957 and 1997, suggesting that recent inputs to the lake are from weathered chlordane sources. PCDD/Fs showed a change in sources from pentachlorophenol (PeCP) in the 1950s and 1960s to combustion sources into the 1990s. Improvements in combustion technology may be responsible for the reducing the proportion of TCDF relative to OCDD in the most recent slice.     

A comparison of sediment quality results with acid volatile sulfide (AVS) and simultaneously extracted metals (SEM) ratio in Vojvodina (Serbia) sediments

The acid-volatile sulfide (AVS), simultaneously extracted metals (SEM), total metals, and pore-water metal concentrations were studied in Vojvodina (Serbia) sediments. In Serbia, there are no regulations concerning sediment quality standards and sediment management. Harmonization of legislation in the domain of environmental protection with EU requirements will increase the significance of the sediment issue. Sediment quality was assessed according to Dutch standards, but the results were also compared with Canadian and USEPA (United States Environmental Protection Agency) guidelines for sediment quality. A comparison of the results based on different criteria for sediment quality assessment shows that they are sometimes contradictory. Therefore, a single approach to quality assessment may be insufficient. The Sigma[SEM]/[AVS] ratio was found to be greater than one at several locations that were already recognized as places of high risk based on Dutch standards. Some other samples had Sigma[SEM]/[AVS]<1, despite of the high risk classification based on the Dutch evaluation. However, not all sediments with Sigma[SEM]/[AVS]>1 can cause increased toxicity because there are many other metal-binding phases in sediments. Metals that are associated with AVS may be released within sediments through storms, dredging activities, oxidation, etc., and may have adverse environmental impacts. This has to be taken into account during dredging, which is for some sediments necessary because the sediment is of class 4 (Dutch evaluation), because the dredging process will certainly increase the concentration of bioavailable heavy metals and disturb the sedimentation dynamics. The obtained results will be invaluable for future activities regarding dredging and sediment management in the country.     

Effect of pH, ionic strength, dissolved organic carbon, time, and particle size on metals release from mine drainage impacted streambed sediments

Acid-mine drainage (AMD) input to a stream typically results in the stream having a reduced pH, increased concentrations of metals and salts, and decreased biological productivity. Removal and/or treatment of these AMD sources is desired to return the impacted stream(s) to initial conditions, or at least to conditions suitable for restoration of the aquatic ecosystem. Some expected changes in the water chemistry of the stream following removal of AMD input include an increase in pH, a decrease in ionic strength, and an increase in dissolved organic carbon (DOC) concentrations from increased biological activity in the absence of toxic metals concentrations. These changes in water chemistry may cause the existing contaminated bed sediments to become a source of metals to the stream water. Streambed sediments, collected from North Fork Clear Creek (NFCC), Colorado, currently impacted by AMD, were assessed for the effects of pH, ionic strength, DOC concentration, time, and particle size on metals release using a factorial design. The design included two levels for each chemical parameter (ionic strength = 40 and 80% lower than ambient; pH = 6 and 8; and DOC = 1 and 3 mg/l higher than ambient), ten sampling times (from zero to 48 h), and two size fractions of sediments (63 μm ≤ x < 2 mm and <63 μm). Greater concentrations of metals were released from the smaller sized sediments compared with the larger, with the exception of Cu. A mild acid digestion (0.6 M HCl) evaluated the amount of each metal that could be removed easily from each of the sediment size fractions. Release of all metals over all time points, treatments, and from both sediment sizes was less than 1% of the extractable concentrations, with the exception of Mn, which ranged from 4 to 7% from the smaller sized sediment. Greater percentages of the 0.6 M HCl-extractable concentrations of Cu, Fe, and Zn were released from the larger sized sediment, while this was true for release of Cd and Mn from the smaller sized sediment. Thus, at least for Cd and Mn, the observed higher concentrations released from the smaller sized sediment with each treatment solution is not simply a function of these particles having higher concentrations available for release, but that these metals also are more readily released from the smaller sediment particles versus the larger. DOC concentration strongly influenced the release of Cu; ionic strength strongly influenced the release of Cd, Mn, and Zn; and interaction effects were observed with the release of Cu, Mn, and Zn from the larger size fraction and with the release of Zn from the smaller size fraction. Overall, results suggest that the expected changes in water chemistry following removal/treatment of the AMD sources would result in a release of metals from the existing sediments, with a greater effect on the release of Cu and Fe, than on the release of Cd, Mn, and Zn.     

A model of microbial activity in lake sediments in response to periodic water-column mixing

Under stagnant conditions, the mass transport of a soluble substrate from a lake's water column to the sediment/water interface is limited by molecular diffusion. Stagnant conditions coupled with a continuing sediment biological demand create a substrate depletion zone above the sediment/water interface. The frequency at which the substrate depletion zone is destroyed by internal seiches and other intermittent flow phenomena influences the time-averaged substrate concentration at the sediment/water interface. A more frequent mixing results in a greater time-averaged interface concentration and consequently affects the amount of microbial biomass that can be supported in the lake sediments and the flux of the substrate into the sediment. A one-dimensional, two-substrate model is used to examine the impact of mixing frequency on the activity of sulfate-reducing bacteria (SRB) in lake sediments. In the model, sulfate is supplied from the water column, while acetate is generated within the sediments. Mass transport to and within the sediments is by molecular diffusion except for instantaneous mixing events. Between mixing events, sulfate concentration gradients form above the sediment/water interface in the diffusive boundary layer. Sulfate depletion zones can be centimeters thick. When typical biological rate and diffusion coefficients for sulfate and acetate are used as inputs, the model indicates that a more frequent water-column mixing results in greater SRB concentrations. For an assumed bulk water-column sulfate concentration of 4.8 mg x l(-1), the sediment SRB concentrations for the modeled hourly, 6-hourly, daily, and weekly mixing frequencies were 175, 136, 91, and 30 mg x m(-2), respectively. The model also predicts higher time-averaged sulfate flux rates at more frequent water-column mixing. The time-averaged sulfate flux rates for the hourly, 6-hourly, daily, and weekly mixing frequencies were 1.26, 1.13, 0.78, and 0.30 mg x m(-2)h(-1), respectively. Thus, mixing frequency can significantly impact microbial activity in lake sediments.     

The erosion behaviour of biologically active sewer sediment deposits: observations from a laboratory study

The erosion behaviour of various fine-grained sediment deposits has been investigated in laboratory experiments. This work mainly focused on tests using sewer sediment in which strong biochemical reactions were observed during the deposit formation period. A small number of initial tests were conducted in which the deposits were made from mixtures of “clean” mineral and organic sediments. The erosion behaviour observed in these tests was compared with the erosion characteristics for sediments taken from deposits in a sewer. The impact of the biological processes on physical properties such as bulk density, water content, deposit structure and the erosive behaviour as a function of bed shear stress are quantified and discussed. Based on these observations it is believed that bio-processes weaken the strength of the in-pipe sediment deposits. A significantly weaker sediment surface layer was observed during deposition under quiescent oxygen-rich conditions. This resulted in a deposit with low shear strength which may be a cause of a first foul flush of suspended sediment when flow rates were increased. Comparison between tests with sewer sediments and the artificial representative surrogates suggested that the deposits of the later did not correctly simulate the depositional development and the resultant erosion patterns observed with the more bio-active sewer sediment.     

Heavy metals in Lake Balaton: water column, suspended matter, sediment and biota

During the period 1999-2002, five sampling cruises have been carried out on Lake Balaton to assess trace metal distribution in the lake and to identify major sources. Eighteen elements, including Cr, Co, Ni, Cu, Zn, Cd, Pb (trace metals) and Al, Ba, Ca, Fe, K, Mg, Mn, Na, P, S, Sr (major metals), were determined in one or more of the lake's compartments. Lower trace metal concentrations in rainwater were observed in June and February 2000, while much higher levels were present in September 2001 (during a storm event) and in snow (February 2000). In the Northern and Western parts of the lake, especially at the inflow of river Zala and the locations of the yacht harbours, metal concentrations were higher in almost all compartments. Because the lake is very shallow, storm conditions also change significantly the metal distributions in the dissolved and particulate phases. The Kis-Balaton protection system located on Zala river functions very efficiently for retaining suspended particulate matter (SPM; 72% retention) and associated metals. Metal concentrations in surface sediments of the lake showed a high variability. After normalisation for the fine sediment fraction, only a few stations including Zala mouth appeared to be enriched in trace metals. In zooplankton, Zn seemed to be much more elevated compared to the other trace metals. Based on the molar ratios of the trace metals in the various compartments and input flows of the lake, several trends could be deduced. For example, molar ratios of the trace metals in the dissolved and solid (suspended particulate matter and sediments) phases in the lake are fairly similar to those in Zala River.