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Ammonium toxicity at high pH in a marine bioassay using Corophium volutator.

Two forms of ammonium exist in water: un-ionized ammonia NH3 and ionized ammonium NH4+. The toxicity to many aquatic organisms is primarily attributed to the NH3 (un-ionized) species, with the NH4+ ion (ionized) species being relatively less toxic. The pH level influences the degree of ionization. It is therefore very important that quality criteria be derived for total ammonium levels at several pH values in order to allow correct interpretation of the sediment bioassay with Corophium volutator. The responses of Corophium to total ammonium were studied in a series of pH-controlled experiments. The LC50 of total ammonium showed a significant decrease with increasing pH, in both water-only and sediment experiments. The results indicated a combined NH4+ and NH3 toxicity at pH levels less than 8.3. The results can be used to set pH-dependent water quality criteria for total ammonium in overlying water in a 10-day sediment bioassay with Corophium volutator.

Amphipoda↗

Exoenzymatic activity and organic matter composition in sediments of the Northern Adriatic Sea: response to a river plume.

Exoenzymatic activities (aminopeptidase and b-glucosidase) and organic matter composition were investigated in June 1996 and February 1997 in the sediment of two areas of the Adriatic Sea differently influenced by the Po river. Protein, carbohydrate, and lipid concentrations were comparable to those reported in most productive systems. Sediment chlorophyll a and biopolymeric carbon concentrations in June were twice as high as in February, but highest exoenzymatic activities and organic matter turnover rates were observed in February (with aminopeptidase activities 10 times higher than in June). The accumulation of organic matter and lower protein and carbohydrate turnover rates observed in June were the result of a different biochemical composition of organic matter in the two sampling periods. In June, organic matter was characterized by a more refractory composition. The consequent reduction of available organic substrate was associated with a decrease in the exoenzymatic substrate affinity. Lower organic matter turnover rates were also observed in deeper sediment layers. In February, the freshwater plume was almost completely confined to the northern area, whereas in June it was extended to the southern area. The results suggest that river inputs influence the biochemical composition and distribution of the sediment organic matter and exoenzymatic activities in coastal marine sediments.

Aminopeptidases↗

Penicillium mycobiota in arctic subglacial ice.

Fungi have been only rarely isolated from glacial ice in extremely cold polar regions and were in these cases considered as random, long-term preserved Aeolian deposits. Fungal presence has so far not been investigated in polar subglacial ice, a recently discovered extreme habitat reported to be inhabited exclusively by heterotrophic bacteria. In this study we report on the very high occurrence (up to 9000 CFU L(-1)) and diversity of filamentous Penicillium spp. in the sediment-rich subglacial ice of three different polythermal Arctic glaciers (Svalbard, Norway). The dominant species was P. crustosum, representing on the average half of all isolated strains from all three glaciers. The other most frequently isolated species were P. bialowiezense, P. chrysogenum, P. thomii, P. solitum, P. palitans, P. echinulatum, P. polonicum, P. commune, P. discolor, P. expansum, and new Penicillium species (sp. 1). Twelve more Penicillium species were occasionally isolated. The fungi isolated produced consistent profiles of secondary metabolites, not different from the same Penicillium species from other habitats. This is the first report on the presence of large populations of Penicillium spp. in subglacial sediment-rich ice.

Arctic Regions↗

Trace metal distribution and enrichment in benthic, estuarine sediments: Southport Broadwater, Australia.

The distribution and enrichment of selected trace metals (Cd, Cr, Cu, Ni, Pb, Sn, Zn) in benthic sediments of the Southport Broadwater, a semi-enclosed coastal body of water adjacent to the Gold Coast city, south-eastern Queensland, Australia, was studied with the objective of assessing the extent and degree of sediment contamination. Sediment samples from the 0-10 cm and 10-20 cm depth intervals of 32 sites within the Southport Broadwater and surrounding residential canals were analysed for particle size distribution, pH, organic C and 'near-total' major (Al, Ca, Fe, Mn) and trace (Cd, Cr, Cu, Ni, Pb, Sn, Zn) metal contents. Sediment contamination for each trace metal was assessed by (1) comparison with Australian sediment quality guidelines, (2) calculation of the index of geoaccumulation based on regional background values, and (3) geochemical normalisation against Al (i.e. the abundance of alumino-silicate clay minerals). Based on this approach, the results indicate that submerged sediments in the study area are not presently enriched with Cd, Cr or Ni, with the spatial distribution of these metals being very well explained by the abundance of alumino-silicate clay minerals. However, several sites were strongly enriched with Cu, Pb, Sn and Zn, arising from sources related to either urban runoff or vessel maintenance activities. The study indicates that several varying approaches are needed for a satisfactory assessment of contaminant enrichment in estuarine sediments.

Aluminum Silicates↗

An evaluation of electrode insertion techniques for measurement of redox potential in estuarine sediments.

E(h) measurements by electrodes are commonly used to characterize redox status of sediments in freshwater, marine and estuarine studies, due to the relative ease and rapidity of data collection. In our studies of fine-grained estuarine seabeds, we observed that E(h) values measured in intact sediment cores were influenced by different electrode insertion techniques. Sediment E(h) measurements generated via lateral insertion of platinum electrodes through silicone-filled ports in acrylic cores were systematically more positive (on the order of 10-100 mV) than profiles generated via vertical insertion of platinum electrodes downward through the sediment-water interface of the same cores. A review of the literature indicated that while researchers routinely use both insertion techniques to measure E(h), no discrepancy in output has previously been reported. We discuss the results of three experiments conducted to determine if the discrepancy in output was caused by electrode poisoning by sulfides during the stepwise vertical insertion technique, or was caused by contact of the electrode with the silicone plug during the lateral insertion technique. We conclude that contact between the platinum surface of the electrode and the silicone plug biases the E(h) measurements, resulting in erroneously positive E(h) values. Insertion of electrodes into sediment through silicone plugs produced E(h) values that were an average of 105.6 mV (+/-10.4 SE) more positive than values generated upon electrode insertion directly into sediment. Thus, we recommend against using an insertion technique where the platinum electrode remains in contact with the silicone plug, as this method results in misclassification of sediment redox state and estimated depth of the redoxcline.

Electrochemistry↗

Depauperate macroinvertebrates in a mine affected stream: clean water may be the key to recovery.

Acid mine drainage (AMD) is frequently linked with changes in macroinvertebrate assemblages, but the relative contribution of water and sediment to toxicity is equivocal. We have shown that the macroinvertebrate fauna of Neubecks Ck, a mine impacted stream in New South Wales, Australia, was much poorer than in two reference streams. Multivariate RELATE analyses indicated that the patterns in the biological data were more strongly correlated with the concentrations of common metals in the surface water than the pore water of these streams. From this we hypothesised that the water was more toxic to the biota than the sediment and we tested this hypothesis with a sediment transplant experiment. Sediment from Neubecks Ck that was placed in reference streams retained high concentrations of metals throughout the experiment, yet supported a macroinvertebrate assemblage similar to that in the reference streams. Sediment from the reference streams that was placed in Neubecks Ck supported few, if any, animals. This indicates that water in Neubecks Ck is toxic to biota, but that sediment is able to support aquatic biota in clean water. Therefore, remediation should focus on improving water quality rather than sediment quality.

Animals↗

Benthic foraminifera and heavy metals distribution: a case study from the Naples Harbour (Tyrrhenian Sea, Southern Italy).

The analysis of 90 surficial sediments from three docks of the Naples Harbour (Levante, Granili, and Diaz) permits to compare the distribution modes of heavy metals with grain sizes, total organic carbon content (TOC) and distribution patterns of benthic foraminifera. Foraminiferal density and species richness decrease with the increasing toxic elements concentrations from the Levante to the Diaz dock. Median concentrations of Ni, Pb, Zn, and Hg (medians of 21.43 mg/kg, 270.24 mg/kg, 489.65 mg/kg, and 1.18 mg/kg, respectively) were reported for the Diaz dock where foraminifera are absent, thus suggesting a possible impact of toxic elements on the benthic ecosystem balance. Compared to the unpolluted marine sediments of the Granili dock, the Levante area shows higher heavy metals levels and a quasi-oligotypic benthic assemblage. This is dominated by the tolerant species Ammonia tepida that may be used as bio-indicator of pollution of anthropised marine sediments.

Animals↗

Partitioning and desorption behavior of polycyclic aromatic hydrocarbons from disparate sources.

Contaminated sediments pose a unique challenge for risk assessment or remediation because the overlying water column may transport contaminants offsite or to ecological receptors. This research compares the behavior of polycyclic aromatic hydrocarbons (PAHs) on marine sediments from two sites. The first site was affected by shipping activities and the second was impacted by a creosote seep. Organic carbon:water partitioning coefficients (Koc values) were measured with three solutions. Desorption was measured using Tenax beads. PAHs from the ship channel had lower Koc values than those from the creosote facility. For example, the average logKoc value of ship channel pyrene was significantly lower than that of creosote facility pyrene (4.39 +/- 0.35 and 5.29 +/- 0.09, respectively, when tested in 5 mM calcium chloride). These results were consistent with the greater desorption of pyrene, phenanthrene and benzo(a)pyrene from the ship channel than from the creosote facility sediments. Organic compound desorption from sediments can be considered to be a two-stage process, with a labile fraction that desorbs quickly and a refractory fraction that desorbs much more slowly. In both sediments, more than 75% of the benzo(a)pyrene was found to have partitioned into the refractory phase. The amounts of phenanthrene and pyrene that partitioned into the refractory phase were lower. Linear correlations of logKoc with log(CR/CL) (where CR and CL are the fractions of the compound in the refractory and labile phases, respectively, at time zero) showed that partitioning measurements made with the US EPA's Toxicity Characteristic Leaching Procedure fluid (US EPA, 1996) most closely matched predictions of desorption behavior. The data imply that with a larger data set, it may be possible to relate simple partitioning measurements to desorption behavior. Partitioning measurements were used to predict water concentrations. Despite having higher concentrations of carcinogenic PAHs [cPAHs, the seven PAHs categorized by the US EPA (2004) as class B2 carcinogens], creosote facility sediments were predicted to produce lower aqueous concentrations of cPAHs. These results indicate that both sediment and contaminant characteristics will impact contaminant release from sediments.

Adsorption↗

Leaching behavior of estuarine sediments and cement-stabilized sediments in upland management environments.

Contaminated surficial sediments in major ports and harbors remain a significant economic liability during routine dredging operations. Numerous beneficial uses have been suggested in recent years that promise reduced sediment management costs concomitant with a productive material use. This manuscript describes the leaching of metals and metalloids from surficial sediments and from controlled low strength material (flowable fill) produced using the estuarine sediments as replacement for sand. Sediments from two locations within the New York/New Jersey Harbor area (Gowanus Canal and Newtown Creek) (USA), were subjected to pH-dependent leaching tests and liquid-to-solid ratio dependent leaching tests. Results indicate that, in general, maximum contaminant levels for drinking water, used here as a benchmark for metals concentrations in leachate, were exceeded only at pH values less than 5 or greater than 9. Leaching as a function of increasing liquid-to-solid ratio demonstrated that pH controlled the observed behavior: unamended sediment leached lower concentrations of all elements except for the oxyanion arsenate. The flowable fill material, despite dilution of the sediment and incorporation into a cementitious matrix, leached higher element concentrations except for arsenic due to the high pH of the material. It was also shown that a much more grossly contaminated material (Newtown Creek) had a very similar leaching behavior to the less contaminated Gowanus Canal material. Speciation calculations demonstrated that dissolved organic carbon plays a significant role in the leaching observed from these estuarine sediments and the flowable fill made with the high organic matter content sediments.

Acids↗

Modelling of flocculation and transport of cohesive sediment from an on-stream stormwater detention pond.

A new model to predict the transport characteristics of suspended sediment from an on-stream stormwater management pond is presented. It is based on Krishnappan's model of flocculated settling in still water, which was extended to dynamic conditions and verified by experiments with stormwater pond sediment in a laboratory rotating flume. The model was derived from first principles, but some input parameters, such as floc properties, had to be obtained by calibration, and input parameters describing flow field properties were obtained from a kappa-epsilon turbulence model. Simulated suspended concentrations vs. time and the size distribution of the flocculated sediment, produced with the calibrated model, agreed well with flume measurements.

Flocculation↗

Long-term effects of phosphorus precipitations with alum in hypereutrophic Lake Süsser See (Germany).

Precipitation and inactivation of phosphorus (P) by the addition of aluminum (Al) is a widely applied lake restoration measure. Many studies about short-term effects are reported, but little is known about long-term effects. To reduce this lack of knowledge we investigated the German hardwater lake, Süsser See, which was treated almost annually from 1977 to 1992 with aluminum sulfate (alum). We conducted sediment core experiments in laboratory, as well as in situ investigations of sediment and pore water. The treatment is clearly recognizable in sediment depth profiles as increases of total phosphorus, NaOH-extractable phosphorus, and NaOH-extractable aluminum. The molar ratio of added Al to additionally bound P is approximately 2.1:1. Pore water profiles of soluble reactive phosphorus taken in situ and in sediment core experiments, as well as sorption batch experiments, illustrate that the Al(OH)3 layer's sorptive capacity is still not exhausted with further P sorption occurring in different P fractions. The P release of the sediment is affected by the magnitude of the downward flux into the P sorbing layer. However, sediment core experiments and a modeling exercise indicate that a buried P sorbing layer has little or no effect on the P release of the uppermost fresh sediment layers.

Alum Compounds↗

Total phosphorus content of river sediments in relationship to calcium, iron and organic matter concentrations.

Data on the total concentrations of phosphorus, calcium, iron and organic matter in surface bed-sediments taken from rivers in the Thames catchment (Wey, Blackwater, Thame and Kennet), the River Swale in Yorkshire (data excludes the organic matter content) as well as the headwaters of the Great Ouse, are collated and compared. Total concentrations of phosphorus, iron and calcium range from 1.7-649, 12-8,333 and 9-4,605 micromol g(-1) (dry weight), respectively, with organic matter in the range of 0.6-19% by dry weight. For the Wey, Blackwater and Great Ouse, sewage inflows had no detectable effect on the sediment concentrations of total calcium, iron and organic matter whereas for the Blackwater and Great Ouse, the total phosphorus contents of the sediment were higher downstream of the effluent input in comparison with a less impacted upstream location. Relationships between the total phosphorus content of the sediments and contents of iron, calcium and organic matter indicated marked differences between the rivers. Although the organic matter content of the sediments was found to be a significant predictor for the total phosphorus concentration for the Blackwater and Great Ouse, the total iron content was also useful for the Blackwater and total calcium for the Great Ouse. It is postulated that this difference is a result of the sediment processes that are known to occur in these two systems, i.e. co-precipitation of phosphate with calcite in the Great Ouse and the formation of vivianite in anoxic sediments of the Blackwater.

Calcium↗

The phosphorus budget of the Thame catchment, Oxfordshire: 2. Modelling.

The phosphorus budget of the River Thame was modelled at a daily time scale, using estimates of diffuse and point source contributions of discharge. The model simulated suspended sediment (SS), soluble unreactive phosphorus (SUP), soluble reactive phosphorus (SRP) and particulate phosphorus (PP) concentrations within the main river and major tributaries. Diffuse source estimates of phosphorus loads were based on characteristic losses from identified main landscape classes, with hydrology described by a simple conceptual storage model. In-stream flow was modelled using a kinematic wave equation. Transfer of suspended sediment and phosphorus components was approximated by advection. In-stream sources and sinks included uptake and release of soluble reactive phosphorus by bed sediment, instant equilibration between SRP and the PP concentration on suspended sediment, and flow-related entrainment and deposition of suspended sediment. Simulations at sites within the catchment were compared with measurements made in 1998-1999. Results showed the P budget is dominated by mixing of diffuse and point source water, but some within-river processes have been shown to be capable of significantly influencing SRP concentrations. The development of a sediment entrainment and deposition component of the model has proved particularly valuable in emulating the hysteretic relationship between discharge and suspended sediment concentration in the river. It also provides a measure of available bed sediment.

England↗

Distribution of long-lived radionuclides of the 238U series in the sediments of a small river in a uranium mineralized region of Spain.

A study is presented on the distribution and mobilization of the natural U isotopes (238U and 234U), 230Th, and 226Ra in the sediments of a small river crossing an uranium mineralized zone where a disused uranium mine is located. Due to the preferential directions for surface run-off waters and to the mine's situation, one sampling point along the river bed was identified as a point of accumulation of radionuclides. The average values of the activity concentrations (Bq/kg) in this sediment sample were 5,025, 5,055, 5,915 and 1,694 for 238U, 234U, 230Th and 226Ra, respectively, while the respective average values of the activity concentrations (Bq/kg) for the sediment sample considered to give the background level were 125, 124, 131 and 370. Isotopic ratios between the descendants of 238U served to clarify some paths of distribution, involving the soils nearest to the sampling points and the location of these points with respect to the disused mine. The differences in behaviour found between the uranium, thorium and radium isotopes were associated to the mobility of these radionuclides in the fluvial system studied. Correlations between the radionuclide activity concentration ratios and stable element concentrations in the sediment samples were also investigated.

Fresh Water↗

Analysis of electrokinetic sedimentation of dredged Welland River sediment.

The Welland River is a tributary of the Niagara River. In the late 1980s it was discovered that a section of the Welland River was contaminated with heavy metals as a results of two sewer outfalls that has been used by a steel plant and local industrial and municipal operations for the last 50-60 years. One of the major problems encountered in the treatment of the dredged Welland River sediment is a slow rate of sedimentation due to the large proportion of fine solids in the sediment. In this study, the results of electrokinetic sedimentation of the Welland River sediment are analyzed based on the principles of gravitational and electrokinetic sedimentation. It was found that the effects of electric field intensity and the initial solid concentration of the suspension are the dominating factors governing the average particle settling velocity, the coefficient of free settling in the free settling stage and the coefficient of sedimentation in the hindered settling stage. The electrokinetic treatment is proven to be effective in terms of increasing the free and hindered settling velocities, reducing the overall sedimentation time and increasing the final solid concentration of the sediment. Thus, electrokinetics can be used to accelerate sedimentation of dilute solid suspensions, such as dredged sediment, wastewater and mine tailings.

Chemical Phenomena↗

Exchange of inorganic phosphate between river waters and bed-sediments.

The kinetics of the release of Soluble Reactive Phosphorus (SRP) in oxic and anoxic conditions and uptake in oxic conditions by contaminated river sediments (River Blackwater in Southern England) were measured using a fluvarium channel operated to mimic environmental conditions. Release rates (from 1 to 10 nmol m(-2) s(-1)) and uptake rates were modeled successfully using a Parabolic equation and Diffuse Boundary Layer model. A SRP release experiment over 61 days showed that large gradients in SRP developed in the porewater as a result of diffusion, sorption, and in-situ generation of SRP in the anoxic zone. This was modeled using a new Triple Zone Model that incorporated diffusion through a liquid boundary layer and sorption/desorption in oxic and anoxic zones. The results highlighted the importance of the oxic zone in controlling the exchange of SRP between the sediment and water column. The model was also applied to explain why the Equilibrium Phosphate Concentration (EPC0) of the sediment measured in oxic conditions was constant (and equal to the value calculated from sorption isotherm measurements) during 2-day release experiments, and also why it increased in the uptake experiments. Measurements in anoxic conditions showed the importance of the sediment temperature in controlling the flux at the interface.

Adsorption↗

Nuclear magnetic resonance and diffuse-reflectance infrared Fourier transform spectroscopy of biosolids-derived biocolloidal organic matter.

We extracted the acid-soluble portion of municipal biosolids, fractionated it by both molecular weight (MW) and hydrophobicity, and used various solid-state nuclear magnetic resonance (NMR) methods and diffuse-reflectance infrared Fourier transform (DRIFT) spectroscopy to characterize the fractions. Spectroscopic characterization of the MW components of the biosolids-derived organic matter fractions revealed the presence of functionally distinct groups of compounds. Quantitative 13C NMR, CH spectral editing, and several two-dimensional NMR experiments show that the high-MW hydrophilic fraction in particular is structurally simple, consisting predominantly of N-acetylated polysaccharides, perhaps derived from bacterial peptidoglycans. In the high-MW hydrophobic fraction, aromatic compounds were present in addition to the N-acetylated polysaccharides. Infrared spectroscopy confirmed that hydrophilic fractions were dominated by carbohydrates and indicated that the lower-MW fractions lacked amide moieties. Complementary interpretations of the DRIFT and NMR spectra improved our knowledge of the components separated by this fractionation scheme, allowing better characterization of biosolids organic matter. Moreover, fractionation based on both MW and hydrophobicity may prove useful in detailed characterization of the structure of biosolids-derived organic matter and other similarly heterogeneous natural organic matter in soils and sediments.

Colloids↗