Millimeter-scale alkalinity measurement in marine sediment using DET probes and colorimetric determination

Constrained DET (Diffusive Equilibration in Thin films) probes equipped with 75 sampling layers of agarose gel (DGT Research^©) were used to sample bottom and pore waters in marine sediment with a 2 mm vertical resolution. After retrieval, each piece of hydrogel, corresponding to 25 μL, was introduced into 1 mL of colorimetric reagent (CR) solution consisting of formic acid and bromophenol blue. After the elution/reaction time, absorbance of the latter mixture was read at 590 nm and compared to a calibration curve obtained with the same protocol applied to mini DET probes soaked in sodium hydrogen carbonate standard solutions. This method allows rapid alkalinity determinations for the small volumes of anoxic pore water entrapped into the gel. The method was assessed on organic-rich coastal marine sediments from Thau lagoon (France). Alkalinity values in the overlying waters were in agreement with data obtained by classical sampling techniques. Pore water data showed a progressive increase of alkalinity in the sediment from 2 to 10 mmol kg⁻¹, corresponding to anaerobic respiration in organic-rich sediments. Moreover, replicates of high-resolution DET profiles showed important lateral heterogeneity at a decimeter scale. This underlines the importance of high-resolution spatial methods for alkalinity profiling in coastal marine systems.     

Potential kinetic availability of metals in sulphidic freshwater sediments

The insolubility of metal sulphides is believed to limit the bioavailability of trace metals in sulphidic sediments. However, if non-equilibrium conditions are important, metals may be more available than simple thermodynamic calculations suggest. To investigate the possible dynamic supply of Cu, Ni and Zn in a sulphidic freshwater sediment, they were measured, along with iron, manganese and sulphide, by the technique of diffusive gradients in thin-films (DGT). DGT measures the supply of solute from sediment to solution in response to a local solute sink. Release of Mn, Cu, Zn and Ni was observed at the sediment surface and attributed to the supply from reductive dissolution of manganese oxides. The depth profile of simultaneously extractable metals (SEM) for Cu and Ni followed the shape of the Mn profile more closely than the profiles of either acid volatile sulphur (AVS) or Fe, again consistent with supply from Mn oxides. Solubility calculations for a mesocosm of homogenised sediment indicated supersaturation with respect to the sulphides of Fe, Cu, Ni and Zn, yet DGT measurements demonstrated a substantial supply of both trace metals and sulphide from the solid phase to the pore waters. Ratios of metals measured in pore waters by DGT were consistent with their release from iron and manganese oxides, indicating that supply, as much as removal processes, determines the pseudo-steady state concentrations in the pore waters. The observations suggest that trace metals are not immediately bound in an insoluble, inert form when they are in contact with sulphide. This has consequences for modelling metal processes in sediment, as well as for uptake by some biota.     

Localised remobilization of metals in a marine sediment

Trace metals and Fe and Mn were measured at vertical spatial resolutions of 2.5 and 5 mm in the top 35 cm of the profundal sediment of a Scottish sea-loch using DGT (diffusive gradients in thin films) technique. DGT probes lower adjacent metal concentrations in pore waters and induce a flux of metal from the solid phase to porewater. The concentrations of metals in porewaters at the interface of the probe were measured during its deployment in a box core. These measurements reflect porewater concentrations of metals and their rates of resupply from the local solid phase of a very small volume (25 microl) of sediment. There was pronounced horizontal and vertical structure in the interfacial concentrations. Horizontal variations were shown by results from adjacent DGT assemblies being markedly different in detail, while vertical structure was measured directly by the DGT-depth profiles. Iron and Mn varied systematically with depth, with both broad and detailed features of Co aligning with those of Mn. There was, however, evidence of additional localised sources of Co that were apparently unrelated to the redox behaviour that Mn typifies, but associated with the remobilization of Ni, possibly from mineral dissolution. Arsenic(III) was remobilized in well-defined zones. Detailed correspondence of As(II) with some Fe features suggest that its release is mechanistically-related to iron oxide dissolution, but the 3 orders of magnitude higher concentrations of Fe may sometimes obscure the association. These results demonstrate that, within sediments, metals may be released in discrete locations that are not measured by conventional porewater sampling techniques due to their horizontal averaging.     

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

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

Dissolved and bioavailable contaminants in the Seine river basin

Diffusive Gradient in Thin Films (DGT) and Semi-Permeable Membrane Devices (SPMDs) were deployed in the Seine river basin in order to assess labile metals and truly dissolved Polycyclic Aromatic Hydrocarbons. We show that the tools are reliable in aquatic environments to assess the speciation of dissolved contaminants and hence provide a good insight into the potential bioavailability of contaminants. The deployment of the DGT and SPMDs in contrasting environments in the Seine river basin allowed distinction to be made of availability of contaminants between headwater streams and much more impacted river reaches and an assessment of bioavailability. At the stations under urban influence, the impact of dissolved organic matter on both copper and PAHs bioavailability is less pronounced than at upstream stations, where humic substances dominate.     

Simultaneous release of sulfide with Fe, Mn, Ni and Zn in marine harbour sediment measured using a combined metal/sulfide DGT probe

The technique of DGT (Diffusive Gradients in Thin Films) was further developed to allow simultaneous measurement of sulfide and trace metals at the same location in sediment. The new combined DGT probe consisted of a layer of gel impregnated with AgI, overlain by (1) a layer of gel containing Chelex, (2) a layer of gel and (3) a filter membrane. Diffusion of sulfide was controlled by layers (1) to (3), while diffusion of metals was controlled by layers (2) and (3). The Chelex gel trapped metals that were measured after elution with acid. The AgI gel trapped sulfide through the formation of Ag2S. This was then measured densitometrically as the colour changed from pale yellow to grey. Experiments demonstrated that concentrations of metal or sulfide measured by the combined device were no different to the concentrations measured by more conventional devices. The presence of Chelex in the gel did not impede the diffusion of sulfide. Deployment of a combined probe in marine sediment revealed simultaneous remobilisation of metals and sulfide at the same location. Solubility calculations indicated that some precipitation of amorphous FeS was probably occurring at the maxima in sulfide concentrations. There was general undersaturation with respect to NiS, but ZnS was supersaturated at all locations. There appeared to be localised active zones of organic matter decomposition, where reduction of manganese oxides, iron oxides and sulfate occurred simultaneously. Mass balance calculations indicated that Ni could not be supplied by release from decomposing organic matter. Manganese oxides were the most likely source, but supply from reductive dissolution of iron oxides could not be entirely discounted. Supply from either Fe or Mn oxides could account for the Zn maxima. Application of the newly developed combined probe provides new information that helps understanding of the complex nature of trace metal and sulfur chemistry in sediments.     

The impact of increased oxygen conditions on metal-contaminated sediments part I: effects on redox status, sediment geochemistry and metal bioavailability

In order to evaluate the effect of improved oxygen concentrations in overlying surface water on the redox status, sediment geochemistry and metal bioavailability in metal-polluted sediments a 54 days lab experiment with two different experimental treatments was conducted (90% and 40% O₂). Changes in redox potential (Eh) in the sediment were monitored over time. At 6 different time points (after 0, 2, 5, 12, 32 and 54 days) and at 4 sediment depths (0-1, 1-4, 4-8 and 8-15 cm), acid volatile sulfides (AVS), simultaneously extracted metals (SEM) and total organic carbon (TOC) were measured and metal release to overlying surface water was determined. Labile metal species in both water and sediment were measured using Diffusive Gradients in Thin films (DGT). Our results showed that elevated oxygen levels in overlying surface water led to an Eh increase in the sediment of the 90% O₂ treatment from 0 to ±200 mV while AVS concentrations in the upper sediment layer decreased by 70%. Following AVS oxidation metal availability in the pore water was highly elevated after 54 days. However, Cu remained strongly bound to the sediment during the whole experiment. Only a limited metal release to the overlying surface water was noticed, which was due to the fact that SEM_tot concentrations in the sediment did not yet exceeded AVS levels ([SEM_tot − AVS]/f_OC = 0) after 54 days. Additionally, adsorption on Fe and Mn hydroxides and particulate organic carbon also slowed down any potential metal release. Our results indicated that increasing oxygen concentrations due to general water quality improvements can enhance the mobility of trace metals which may result in the leaching of sediment-bound metals to overlying surface water, even in undisturbed watercourses.     

Estimates of benthic fluxes of nutrients across the sediment-water interface (Guarapiranga reservoir, São Paulo, Brazil)

Concentration profiles of nutrients (dissolved organic carbon, nitrate, nitrite, ammonium and soluble reactive phosphorus) were determined in pore waters from sediment from the Guarapiranga reservoir (S?o Paulo, Brazil). Redox potential and acid volatile sulfide measurements on bulk sediment samples were determined in the field and laboratory, respectively. The sediment redox potential ranged from -170 to -220 mV at 0-1 cm and increased to somewhat higher values at 20 cm. The acid volatile sulfide (AVS) profile had a bimodal pattern with concentration peaks at 3 cm (27-55 mg kg(-1)) and 14 cm (70-110 mg kg(-1)). Dissolved organic carbon (DOC) concentrations increased from the surface (4.7-5.6 mg l(-1)) to 20 cm (values up to 12 mg l(-1)). The concentration of ammonium increased significantly with depth, with maximum concentrations occurring at 15 cm; nitrate-nitrite concentrations only increased appreciably at 10 cm. The SRP profiles increased in concentration from the surface to approximately 10-cm depth, with a maximum value of 1200 microg H2PO4- l(-1). Benthic fluxes from the sediment into the pore water ranged from 278 to 339 mg cm(-2) year(-1) for ammonium ions and from 8 to 18 mg cm(-2) year(-1) for SRP. These upward diffusive fluxes correspond to 47-70% and to 10-24% of the total deposition of N and P measured in the reservoir, respectively. The burial rates for N and P in these sediments are 30-54% and 76-89%, respectively.     

Mercury cycling between the water column and surface sediments in a contaminated area

Mercury cycling in the water column and upper sediments of a contaminated area, the Largo do Laranjo, Aveiro (Portugal), was evaluated after determination of reactive and non-reactive mercury concentrations in the water column and pore waters of sediments, collected in several places of this bay. In the water column, reactive mercury concentrations varied between 10 and 37 pmol dm(-3), the highest values being observed near the mercury anthropogenic source. However, reactive mercury was a narrowly constrained fraction of the total mercury, making up only 4-16% of the total, showing evidence of the importance of dissolved organic matter on mercury transport. In sediments, higher concentrations of mercury were also determined near industrial discharges. Results indicate the existence of an equilibrium between solid and liquid phases, determined by solid sediment/pore water distribution coefficients. Much of the mercury present in the solid fraction is associated with organic matter (r=0.837) and iron oxyhydroxides (r=0.919), but as oxides begin to dissolve in reduced sediments and organic matter decays, the adsorbed mercury is released. In fact, the mercury concentrations in pore waters of those contaminated sediments largely exceeded the values determined in the water column. As molecular diffusion may contribute to the dissolved mercury distribution in the overlying water column, this phenomenon was evaluated. However, the pore waters of Largo do Laranjo do not enrich the water column substantially in terms of reactive and non-reactive mercury. In fact, pore waters can contribute only to 0.2% and 0.5% of the reactive and non-reactive mercury present in the water column, respectively, showing that as long as mercury is being incorporated in sediments, it stays in stable forms.     

Groundwater geochemistry and its implications for arsenic mobilization in shallow aquifers of the Hetao Basin, Inner Mongolia

Arsenic concentrations in shallow groundwaters from the Hetao Basin of Inner Mongolia range between 0.6 and 572 microg/L. High As groundwaters generally occur in the shallow alluvial-lacustrine aquifers, which are mainly composed of black (or dark grey) fine sands in a reducing environment. They are characterized by high concentrations of dissolved Fe, Mn, HCO(3)(-), P and S(2-), and low concentrations of NO(3)(-) and SO(4)(2-). Low SO(4)(2-) coupled with high S(2-) suggests that SO(4)(2-) reduction has been an active process. In the reducing groundwaters, inorganic As(III) accounts for around 75% of total dissolved As. Total As contents in the sediments from three representative boreholes are observed to be 7.3-73.3 mg/kg (average of 18.9 mg/kg). The total As is mildly-strongly correlated with total Fe and total Mn, while a quite weak correlation exists between total As and total S, suggesting that the As is associated with Fe-Mn oxides, rather than sulfides in the sediments. It is found in the sequential extraction that chemically active As is mainly bound to Fe-Mn oxides, up to 3500 microg/kg. The mobilization of As under reducing conditions is believed to include reductive dissolution of Fe-Mn oxides and reduction of adsorbed As. Although exchangeable As is labile and very vulnerable to hydrogeochemical condition, the contribution is relatively limited due to the low concentrations. The competition between As and other anions (such as HPO(4)(2-)) for binding sites on Fe-Mn oxides may also give rise to the release of As into groundwater. Slow groundwater movement helps accumulation of the released As in the groundwaters.     

Comparison of diffusive gradients in thin films and equilibrium dialysis for the determination of Al, Fe(III) and Zn complexed with dissolved organic matter

The distinction between 'free' metals and organically complexed metals in aqueous solutions is important for research involving the mobility or bioavailability of metals in the environment. In this study, the applicability of equilibrium dialysis (molecular weight cut-off = 1000 Da) and diffusive gradients in thin films (DGT) to determine 'free' Al, Fe(III) and Zn in four forest soil solutions was compared. The 'free' metals as measured by both methods, consist of hydrated metal cations and soluble inorganic metal complexes. In addition, dialysis measures any organic complexes < 1000 Da and DGT measures a portion of smaller labile organic complexes. The four soil solutions were prepared by water extraction of an organic soil horizon (H) from a Fimic Anthrosol, and contained either 20 or 75 mg C/l dissolved organic matter at pH 4.0 and pH 7.0. To test the performance of both methods and optimize experimental volume and time, experiments using metal nitrate solutions were carried out. In the solutions at pH 4.0, no significant differences in average 'free' metal contents were found for Al, Fe(III) or Zn. This makes DGT a viable alternative for equilibrium dialysis for the study of the complexation of all three metals in acidic soils. At pH 7.0, again no significant difference between both methods were found for Al and Fe(III), but the DGT results for Zn were significantly higher. This was likely caused by labile organic complexes that were only detected by DGT.     

High-resolution profiles of trace metals in the pore waters of riverine sediment assessed by DET and DGT

The techniques of DET (diffusive equilibrium in thin films) and DGT (diffusive gradients in thin films) were applied to obtain high-resolution vertical profiles of trace metals in freshwater sediments. In the framework of the EU-Interreg project Stardust (http://www.vliz.be/projects/stardust/) between France and Belgium, in which the mobility of sediment bound metals is investigated, sediment samples were collected from the Upper Scheldt River (at Helkijn, Belgium) and the Leie River (at Warneton, located at the Belgian-French border). Intra- and inter-laboratory comparisons of the gel techniques were carried out between the two laboratories involved. In general, a good agreement was observed, taking sediment heterogeneity into account. At both stations, metal pore water profiles show more or less similar tendencies although the sediment at Warneton was more anoxic than at Helkijn. A strong correlation between Fe and Co was found at Helkijn as well as at Warneton. The metal gradients at the water/sediment interface were calculated from the high resolution profiles and the conventional, low resolution profiles. Significant differences were observed.     

The influence of the abandoned Kalecik Hg mine on water and stream sediments (Karaburun,Izmir, Turkey)

This study covers the geochemical investigations on water and stream sediments to evaluate the influence from the abandoned Kalecik Hg mine. The groundwater samples (S5, S8, S9, WW10) are neutral, slightly alkaline waters which have pH values varying between 7.3 and 7.5. Electrical conductivity (EC) values of groundwaters for spring samples are low (250-300 microS/cm). However, groundwater obtained from a deep well has a higher EC value of 950 microS/cm. Hg concentrations of groundwater samples vary between 0.01 and 0.13 microg/l. Hg concentrations of other water samples taken from mining area from surface waters and adits are between 0.10 and 0.99 microg/l. Adit water (A4) collected at the mine has the highest Hg content of 0.99 microg/l and a pH of 4.4. Trace element concentrations of mine water samples show variable values. As is observed only in MW1 (310 microg/l). A4 was enriched in Cd, Co and Cr and exceed the Turkish drinking water standards (Türk Standartlari Enstitüsü, 1997). Cu concentrations vary between 6.0 and 150 microg/l and are below the Turkish water standards. Mn concentrations in mine waters are between 0.02 and 4.9 mg/l. Only for sample A4 Mn value (4.9 mg/l) exceeds the standard level. Ni was enriched for all of the mine water samples and exceeds the safe standard level (20 microg/l) for drinking water. Of the major ions SO(4) shows a notable increase in this group reaching 650 mg/l that exceeds the drinking water standards. Stream sediment samples have abnormally high values for especially Hg and As, Sb, Ni, Cr metals. With the exception of sample Ss6 of which Hg concentration is 92 mg/kg, all the other samples have Hg contents of higher than 100 mg/kg. Pollution index values are significantly high and vary between 69 and 82 for stream sediment samples.     

Variation of manganese, dissolved oxygen and related chemical parameters in the bottom waters of Lake Mendota, Wisconsin

The increase of Mn concentration and the simultaneous depletion of dissolved oxygen in the bottom waters (hypolimnion) of Lake Mendota, Wisconsin were studied in situ. Considerably higher Mn concentrations were found in the hypolimnion compared to Fe, despite a sedimentary Fe/Mn weight ratio of 19 : 1. Laboratory equilibration studies under anoxic conditions indicated that pH was an important parameter involved in the release of Mn from the sediments. This was also implied by the Mn and pH data measured in situ. Possible mechanisms involved in the release of Mn from the sediments including desorption of Mn from oxide substrates, reduction of Mn oxides and dissolution of carbonates and sulfides are discussed.     

Mineralogical and geochemical controls of arsenic speciation and mobility under different redox conditions in soil, sediment and water at the Mokrsko-West gold deposit, Czech Republic

Naturally contaminated soil, sediment and water at the Mokrsko-West gold deposit, Central Bohemia, have been studied in order to determine the processes that lead to release of As into water and to control its speciation under various redox conditions. In soils, As is bonded mainly to secondary arseniosiderite, pharmacosiderite and Fe oxyhydroxides and, rarely, to scorodite; in sediments, As is bonded mainly to Fe oxyhydroxides and rarely to arsenate minerals.The highest concentrations of dissolved As were found in groundwater (up to 1141 μg L^− 1), which mostly represented a redox transition zone where neither sulphide minerals nor Fe oxyhydroxide are stable. The main processes releasing dissolved As in this zone are attributed to the reductive dissolution of Fe oxyhydroxides and arsenate minerals, resulting in a substantial decrease in their amounts below the groundwater level. Some shallow subsurface environments with high organic matter contents were characterized by reducing conditions that indicated a relatively high amount of S^− 2,0 in the solid phase and a lower dissolved As concentration (70-80 μg L^− 1) in the pore water. These findings are attributed to the formation of Fe(II) sulphides with the sorbed As. Under oxidizing conditions, surface waters were undersaturated with respect to arsenate minerals and this promoted the dissolution of secondary arsenates and increased the As concentrations in the water to characteristic values from 300 to 450 μg L^− 1 in the stream and fishpond waters. The levels of dissolved As(III) often predominate over As(V) levels, both in groundwaters and in surface waters. The As(III)/As(V) ratio is closely related to the DOC concentration and this could support the assumption of a key role of microbial processes in transformations of aqueous As species as well as in the mobility of As.     

In situ measurements of labile Cu, Cd and Mn in river waters using DGT

The technique of diffusive gradients in thin-films (DGT) has been trialed in two river systems for in situ trace metal speciation measurements. This paper presents results for cadmium, copper and manganese concentrations in fresh and estuarine waters and demonstrates for the first time the effectiveness of using DGT to measure labile metal concentrations in such waters. This work has shown that even with very simple deployment systems the technique is sensitive and reproducible. The precision of in situ DGT measurements was typically 11% or better when the precision of subsequent analysis was good. The in-built metal pre-concentration procedure of DGT allowed Cd to be measured at concentrations below the detection limit of a direct determination by GF-AAS. The theoretically predicted linear increase in mass with time was obtained in river deployments of up to 72 h, confirming steady state river conditions and indicating no adverse effects due to biofouling over this period. Concentrations of DGT-labile Cu and Cd were equal to dissolved (0.45 micron) metal concentrations for the Ring and Stitt Rivers indicating the absence of tightly bound organic complexes or colloidal species. DGT-labile Cu and Cd were approximately 50% of the dissolved metal in the Que River and DGT-labile Cu was approximately 30% of dissolved Cu in the Savage River. A concentration-depth profile of labile manganese was obtained in a stratified estuary by deployment of a string of DGT devices at 0.3-m intervals across the redoxcline. Results revealed a large spike (maximum concentration = 1.4 mg/l) of DGT-labile Mn at the base of the redoxcline and demonstrate the utility of DGT to determine vertical changes in metal speciation across redox boundaries in stratified estuarine systems. It is in such dynamic systems as this that the in situ capabilities of DGT are likely to be most useful. DGT records multiple metal species as they exist in situ, overcoming the considerable problems of contamination often associated with sample collection and handling.     

Lake sedimentary evidence of phosphorus,iron and manganese mobilisation from intensively fertilised soils

A study of historical P inputs to Friary Lough, Co. Tyrone, Northern Ireland used a multi-sediment core approach. One of the sediment cores taken from the littoral zone at 2.5m water depth showed exceptionally high P, Fe and Mn concentrations below 20 cm sediment depth. Concentrations increased to 14 mg Pg(-1), 238 mg Feg(-1) and 35 mg Mng(-1) in the sediment profile and compared with deep basin maxima of 7 mg Pg(-1), 70 mg Feg(-1) and 2 mg Mng(-1) in surface sediments at 8.5m water depth. It is proposed that the high concentrations in the littoral zone core are due to post-depositional intrusion of chemical-rich local groundwater from soils in adjacent fields that are excessively fertilised with organic slurry. Soil analyses showed Olsen-P concentrations in these fields up to 125 mgkg(-1) at the soil surface (0-7.5 cm) and 39 mgkg(-1) in the sub-soil at 20 cm depth. We suggest that the mobilisation of P, Fe and Mn is due to leaching following P saturation and/or the loss of P absorbing chemicals due to prolonged reduction and complexing in wet soils. Further work will explore this relationship and the nature of the hydrological pathways through soil.     

Correlations, partitioning and bioaccumulation of heavy metals between different compartments of Lake Balaton

Correlations between trace metals in dissolved and particulate phases, zooplankton, mussels and sediments in Lake Balaton were investigated. The degree of correlation between the various metals was different in each of the investigated compartments. Particulate metal concentrations (microg g(-1)) were anti-correlated with suspended particulate matter (SPM) (mg l(-1)), indicating a dilution effect, while total metal concentrations in the water column (microg l(-1)) were highly correlated with SPM, implying a major influence of the turbidity on the total metal concentrations. Between compartments, not many significant correlations were recognized. Only Ba, Ca, Sr and Mg are correlated in the sediments and in the particulate phase, suggesting common sources for both compartments. Partitioning coefficients (Kd) of trace metals between dissolved and particulate phases are generally low, typical for natural water and fairly stable over the lake. Most of the trace metals (Zn, Co, Cd and Pb) exist in the particulate phase (for about 70% of the total metal load). Cu and Ni are exceptions, showing a more equal distribution. Bioconcentration factors (BCF) of zooplankton and mussels were comparable to those of other natural waters. A negative biomagnification from suspended particulate matter to zooplankton and from sediment to mussel was recognized for all trace metals, except a small enrichment of Zn in zooplankton and Cd in mussel. Four factors were recognized in SPM and in sediments but they did not contain the same group of metals. Cluster analysis showed that metal accumulations in the sediments were different between northern and southern shores and in SPM between western and eastern areas.     

Oxidation of arsenite in groundwater using ozone and oxygen

Oxidation of arsenite [As(III)] with ozone and oxygen was investigated in groundwater samples containing 46-62 micrograms/l total dissolved arsenic, 100-1130 micrograms/l Fe and 9-16 micrograms/l Mn. Conversion of As(III), which constituted over 70% of dissolved arsenic in the samples, to As(V) was fast with ozone, but sluggish with pure oxygen and air. Iron and manganese in the samples were also oxidized and, by sequestering the resultant As(V), played a significant role in the rate of reaction. Sorption capacity of freshly precipitated Fe(OH)3 was estimated to be 15.3 mg As/g. The kinetics of As(III) oxidation were interpreted using modified pseudo-first-order reaction. Half-lives of As(III) in experimental solutions involving saturation with each gas were approximately 4 min for the ozone reaction and, depending on the Fe concentrations, 2-5 days for pure oxygen and 4-9 days for air.     

Sulfolane biodegradation potential in aquifer sediments at sour natural gas plant sites

Sulfolane is used in the treatment of sour natural gas. It is a highly water soluble compound that has been introduced into soils and groundwaters at a number of sour gas processing plant sites. Aquifer sediments from contaminated locations at three sites in western Canada were assessed for microbial activity and their ability to degrade sulfolane under aerobic and five anaerobic (nitrate-, Mn(IV)-, Fe(III)-, sulfate- and CO₂-reducing) conditions. The microcosms were supplemented with 200 mg/L sulfolane and adequate supplies of N, P, and the appropriate terminal electron acceptor. Microcosms containing contaminated aquifer sediments from each of the three sites were able to degrade sulfolane aerobically at 8°C and 28°C, and the biodegradation followed zero-order kinetics. The lag times before the onset of sulfolane biodegradation were shorter when sulfolane-contaminated sediments were used as inocula than when uncontaminated soils were used. No anaerobic sulfolane biodegradation was observed at 28°C, nor was sulfolane biodegradation observed at 8°C under Fe(III)-, sulfate- and CO₂-reducing conditions. At 8°C, anaerobic degradation of sulfolane coupled to Mn(IV) reduction was observed in microcosms from two sites, and degradation coupled to nitrate reduction was seen in a microcosm from one of the contaminated sites.