Remediation of contaminated marine sediment using thin-layer capping with activated carbon--a field experiment in Trondheim harbor, Norway

In situ amendment of contaminated sediments using activated carbon (AC) is a recent remediation technique, where the strong sorption of contaminants to added AC reduces their release from sediments and uptake into organisms. The current study describes a marine underwater field pilot study in Trondheim harbor, Norway, in which powdered AC alone or in combination with sand or clay was tested as a thin-layer capping material for polycyclic aromatic hydrocarbon (PAH)-contaminated sediment. Several novel elements were included, such as measuring PAH fluxes, no active mixing of AC into the sediment, and the testing of new manners of placing a thin AC cap on sediment, such as AC+clay and AC+sand combinations. Innovative chemical and biological monitoring methods were deployed to test capping effectiveness. In situ sediment-to-water PAH fluxes were measured using recently developed benthic flux chambers. Compared to the reference field, AC capping reduced fluxes by a factor of 2-10. Pore water PAH concentration profiles were measured in situ using a new passive sampler technique, and yielded a reduction factor of 2-3 compared to the reference field. The benthic macrofauna composition and biodiversity were affected by the AC amendments, AC + clay having a lower impact on the benthic taxa than AC-only or AC + sand. In addition, AC + clay gave the highest AC recoveries (60% vs 30% for AC-only and AC + sand) and strongest reductions in sediment-to-water PAH fluxes and porewater concentrations. Thus, application of an AC-clay mixture is recommended as the optimal choice of the currently tested thin-layer capping methods for PAHs, and more research on optimizing its implementation is needed.     

Storm disturbance of sediment contaminants at a hot-spot in the Baltic Sea assessed by 234Th radionuclide tracer profiles

Fly ash sludges from an abandoned metal smelter were dumped into the shallow inner part of the Mecklenburg Bay until 1971, representing the most severe heavy metal contamination hot-spot along the German coast. Half of the dumped Zn (455 t) and Pb (173 t) inventory was found to be spread from the originally 0.5 km2 hot-spot site to a now 360 km2 affected adjacent area. Wave-driven resuspension during gale events produced large pulses of contaminated sediments from this hot-spot due to the only 23 m water depth. Instantaneous sediment mixing down to 10 cm occurs during such a wave event as evidenced by activity profiles of the short-lived radionuclide 234Th in sediment cores. According to these estimated sediment exchange fluxes in the transport bottom area, each wave event may have mobilized Zn and Pb pulses on the order of several hundreds of kilograms from the dump site, sufficient to build up a plume in sediments of the outer bay area. With each centimeter (approximately 5 yr) of additional natural sediment capping, however, the amount of metal remobilization would decrease by about 50%.     

DGT-Induced Copper Flux Predicts Bioaccumulation and Toxicity to Bivalves in Sediments with Varying Properties

Many regulatory frameworks for sediment quality assessment include consideration of contaminant bioavailability. However, the "snap-shots" of metal bioavailability provided by analyses of porewaters or acid-volatile sulfide-simultaneously extractable metal (AVS-SEM) relationships do not always contribute sufficient information. The use of inappropriate or inadequate information for assessing metal bioavailability in sediments may result in incorrect assessment decisions. The technique of diffusive gradients in thin films (DGT) enables the in situ measurement of metal concentrations in waters and fluxes from sediment porewaters. We utilized the DGT technique to interpret the bioavailability of copper to the benthic bivalve Tellina deltoidalis in sediments of varying properties contaminated with copper-based antifouling paint particles. For a concentration series of copper-paint contaminated sandy, silty-sand, and silty sediment types, DGT-probes were used to measure copper fluxes to the overlying water, at the sediment-water interface, and in deeper sediments. The overlying water copper concentrations and DGT-Cu fluxes were shown to provide excellent exposure concentration-response relationships in relation to lethal effects occurring to the copper-sensitive benthic bivalve, T. deltoidalis. The study demonstrates the strength of the DGT technique, which we expect will become frequently used for assessing metal bioavailability in sediments.     

Long-term recovery of PCB-contaminated surface sediments at the Sangamo-westonl Twelvemile Creek/lake Hartwell Superfund Site

Natural recovery of contaminated sediments relies on burial of contaminated sediments with increasingly clean sediments over time (i.e., natural capping). Natural capping reduces the risk of resuspension of contaminated surface sediments, and it reduces the potential for contaminant transport into the food chain by limiting bioturbation of contaminated surface or near-surface sediments. This study evaluated the natural recovery of surface sediments contaminated with polychlorinated biphenyls (PCBs) at the Sangamo-Weston/Twelvemile Creek/Lake Hartwell Superfund Site (Lake Hartwell), Pickens County, SC. The primary focus was on sediment recovery resulting from natural capping processes. Total PCB (t-PCB), lead-210 (210Pb), and cesium-137 (137Cs) sediment core profiles were used to establish vertical t-PCB concentration profiles, age date sediments, and determine surface sedimentation and surface sediment recovery rates in 18 cores collected along 10 transects. Four upgradient transects in the headwaters of Lake Hartwell were impacted by historical sediment releases from three upgradient sediment impoundments. These transects were characterized by silt/ clay and sand layering. The highest PCB concentrations were associated with silt/clay layers (1.8-3.5% total organic carbon (TOC)), while sand layers (0.05-0.32% TOC) contained much lower PCB concentrations. The historical sediment releases resulted in substantial burial of PCB-contaminated sediment in the vicinity of these four cores; each core contained less than 1 mg/kg t-PCBs in the surface sand layers. Cores collected from six downgradient Lake Hartwell transects consisted primarily of silt and clay (0.91-5.1% TOC) and were less noticeably impacted by the release of sand from the impoundments. Vertical t-PCB concentration profiles in these cores began with relatively low PCB concentrations at the sediment-water interface and increased in concentration with depth until maximum PCB concentrations were measured at approximately 30-60 cm below the sediment-water interface, ca. 1960-1980. Maximum t-PCB concentrations were followed by progressively decreasing concentrations with depth until the t-PCB concentrations approached the detection limit, where sediments were likely deposited before the onset of PCB use at the Sangamo-Weston plant. The sediments containing the maximum PCB concentrations are associated with the period of maximum PCB release into the watershed. Sedimentation rates averaged 2.1 +/- 1.5 g/(cm2 yr) for 12 of 18 cores collected. The 1994 Record of Decision cleanup requirement is 1.0 mg/kg; two more goals (0.4 and 0.05 mg/kg t-PCBs) also were identified. Average surface sedimentation requirements to meet the three goals were 1.4 +/- 3.7, 11 +/- 4.2, and 33 +/- 11 cm, respectively. Using the age dating results, the average recovery dates to meet these goals were 2000.6 +/- 2.7, 2007.4 +/- 3.5, and 2022.7 +/- 11 yr, respectively. (The 95% prediction limits for these values also are provided.) Despite the reduction in surface sediment PCB concentrations, PCB concentrations measured in largemouth bass and hybrid bass filets continue to exceed the 2.0 mg/kg FDA fish tolerance level.     

Use of life cycle assessments to evaluate the environmental footprint of contaminated sediment remediation

Ecological and human risks often drive the selection of remedial alternatives for contaminated sediments. Traditional human and ecological risk assessment (HERA) includes assessing risk for benthic organisms and aquatic fauna associated with exposure to contaminated sediments before and after remediation as well as risk for human exposure but does not consider the environmental footprint associated with implementing remedial alternatives. Assessment of environmental effects over the whole life cycle (i.e., Life Cycle Assessment, LCA) could complement HERA and help in selecting the most appropriate sediment management alternative. Even though LCA has been developed and applied in multiple environmental management cases, applications to contaminated sediments and marine ecosystems are in general less frequent. This paper implements LCA methodology for the case of the polychlorinated dibenzo-p-dioxins and -furans (PCDD/F)-contaminated Grenland fjord in Norway. LCA was applied to investigate the environmental footprint of different active and passive thin-layer capping alternatives as compared to natural recovery. The results showed that capping was preferable to natural recovery when analysis is limited to effects related to the site contamination. Incorporation of impacts related to the use of resources and energy during the implementation of a thin layer cap increase the environmental footprint by over 1 order of magnitude, making capping inferior to the natural recovery alternative. Use of biomass-derived activated carbon, where carbon dioxide is sequestered during the production process, reduces the overall environmental impact to that of natural recovery. The results from this study show that LCA may be a valuable tool for assessing the environmental footprint of sediment remediation projects and for sustainable sediment management.     

Assessing the effectiveness of thin-layer sand caps for contaminated sediment management through passive sampling

The effectiveness of thin-layer sand capping for contaminated sediment management (capping with a layer of thickness comparable to the depth of benthic interactions) is explored through experiments with laboratory-scale microcosms populated with the deposit-feeding oligochaete, Ilyodilus templetoni. Passive sampling of pore water concentrations in the microcosms using polydimethylsiloxane (PDMS)-coated fibers enabled quantification of high-resolution vertical concentration profiles that were used to infer contaminant migration rates and mechanisms. Observed concentration profiles were consistent with models that combine traditional contaminant transport processes (sorption-retarded diffusion) with bioturbation. Predictions of bioaccumulation based on contaminant pore water concentrations within the surface layer of the cap correlated well with observed bioaccumulation (correlation coefficient of 0.92). The results of this study show that thin-layer sand caps of contaminated sediments can be effective at reducing the bioaccumulation of polycyclic aromatic hydrocarbons (PAHs) provided the thickness of the cap layer exceeds the depth of organism interaction with the sediments and the pore water concentrations within the biologically active zone remain low (e.g., when molecular diffusion controls transport from the underlying sediment layer).     

Spatial and temporal evolution of biogeochemical processes following in situ capping of contaminated sediments

In situ capping has recently emerged as a remedial method for contaminated sediments and involves placing a layer of clean material at the sediment-water interface. The biogeochemical response of native sediment following capping, as well as the redoxenvironmentsthatdevelopwithinthe cap, are currently unknown. Column experiments were performed using voltammetric microelectrodes to characterize spatial and temporal distributions of biogeochemical processes in capped sediments under stagnant and upflow conditions. Oxygen penetration into sand caps extended only a few centimeters, thus maintaining underlying sediment anaerobic. Chemical species indicative of heterotrophic organic matter degradation (Mn2+, Fe2+, organic--FeIII(aq), FexSy(aq), sigmaH2S) were observed in stratified zones below the oxic layer. The majority of the overlying cap was subject to iron-reducing conditions under stagnant flow, while upflow conditions led to a compression of the redox zones toward the cap-water interface. Controls confirmed that sediment capping induced an upward, vertical shift of biogeochemical processes into the overlying cap, with redox stratification conserved. The redox conditions within the cap, specifically the predominance of iron reduction, should allow for reductive contaminant attenuation processes to extend into the overlying cap. These findings improve our understanding of the dynamics of biogeochemical processes following capping of contaminated sediments.     

Advection dominated transport of polycyclic aromatic hydrocarbons in amended sediment caps

Typical sand caps used for sediment remediation have little sorption capacity to retard the migration of hydrophobic contaminants such as PAHs that can be mobilized by significant groundwater flow. Laboratory column experiments were performed using contaminated sediments and capping materials from a creosote contaminated USEPA Superfund site. Azoic laboratory column experiments demonstrated rapid breakthrough of lower molecular weight PAHs when groundwater seepage was simulated through a column packed with coarse sand capping material. After eight pore volumes of flow, most PAHs measured showed at least 50% of initial source pore water concentrations at the surface of 65 cm capping material. PAH concentration in the cap solids was low and comparable to background levels typically seen in urban depositional sediment, but the pore water concentrations were high. Column experiments with a peat amendment delayed PAH breakthrough. The most dramatic result was observed for caps amended with activated carbon at a dose of 2% by dry weight. PAH concentrations in the pore water of the activated carbon amended caps were 3-4 orders of magnitude lower (0.04 ± 0.02 μg/L for pyrene) than concentrations in the pore water of the source sediments (26.2 ± 5.6 μg/L for pyrene) even after several hundred pore volumes of flow. Enhancing the sorption capacity of caps with activated carbon amendment even at a lower dose of 0.2% demonstrated a significant impact on contaminant retardation suggesting consideration of active capping for field sites prone to groundwater upwelling or where thin caps are desired to minimize change in bathymetry and impacts to aquatic habitats.     

Historical perspective of industrial lead emissions to the atmosphere from a Canadian smelter

Dated sediment cores from four remote Canadian Shield headwater lakes, where atmospheric deposition has been the only input of anthropogenic Pb, situated along a transect extending 300 km from a nonferrous metal smelter, were analyzed for both lead concentrations and isotopic composition; porewater samples collected at the same sites were analyzed for Pb and other geochemical variables. The depth distributions of stable Pb isotope ratios show the presence of several isotopically distinct Pb types since the preindustrial period. Lead from the smelter emissions had an isotopic signature (e.g., 206Pb/207Pb approximately 0.993) that was clearly distinct from those of Pb in aerosols collected at sites remotefrom point sources in Eastern Canada (e.g., 206Pb/207Pb usually approximately 1.15-1.20) and the United States (e.g., 206Pb/207Pb usually approximately 1.15-1.22), allowing the geographical area impacted by the smelter Pb emissions to be traced. On the basis of the sediment Pb isotopic composition, it is estimated that lead from the smelter accounts for 89%, 88%, and 5-34% of the total inventory of anthropogenic Pb deposited in the sediments of lakes located 10, 25, and 150 km from the smelter, respectively; but lead from this point source was not detected in sediments of a fourth lake that is 300 km from the smelter. We also estimate that the amount of smelter-derived Pb deposited within a distance of 150 km is equivalent to 5-10% of the amount released by leaded gasoline combustion in all of Canada. Sharp decreases in the recent Pb fluxes to lake sediments indicate that the measures taken to mitigate metal emissions from the smelter were effective.     

Bioaccumulation and toxic potencies of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in tidal flat and coastal ecosystems of the Ariake Sea,Japan

Sediment and marine biota comprising several species of tidal flat and coastal organisms were analyzed for polychlorinated biphenyls (PCBs) including non- and mono-ortho coplanar congeners and polycyclic aromatic hydrocarbons (PAHs) to examine bioaccumulation profiles and toxic potencies of these contaminants. Concentrations of PCBs in tidal flat organisms ranged from 3.6 ng/g (wet wt) in clams to 68 ng/g (wet wt) in omnivore tidal flatfishes, a discernible trend reflecting concentrations and trophic levels. In contrast, PAHs concentrations were the highest in lower trophic organisms, such as crabs and lugworms from tidal flat, whereas those in coastal fishes, squid, and finless porpoises were less than detection limit. Greater bioaccumulation of PAHs was found in lugworms and crabs, which might be due to their direct ingestion of sediment particulates absorbed with PAHs. TCDD toxic equivalents (TEQs) were calculated for PCBs and PAHs in sediments and biota. PCBs accounted for a greater proportion of total TEQs (sum(TEQs): sum of TEQ(PCB) and TEQ(PAH)) in coastal and tidal flatfishes (>95%), while PAHs occupied a considerable portion of sum(TEQs) in sediment (>97%). Interestingly, TEQ(PAH) accounted for 37% and 81% of the sum(TEQs) in crabs and clams, respectively. Benzo[b]fluoranthene was the dominant contributor to TEQ(PAH) in both the species. Considering these observations, the environmental risks of PAHs may not be ignored in benthic tidal flat organisms due to their greater bioaccumulation through sediments.     

Assessment of nontoxic, secondary effects of sorbent amendment to sediments on the deposit-feeding organism Neanthes arenaceodentata

Activated carbon (AC) amendments to sediments were tested for nontoxic, secondary effects on survival, weight change, and energetic biomarkers of the deposit feeder Neanthes arenaceodentata. The tests employed silica sand, reference sediments, and contaminated sediments. Survival was not affected by the sediment type, the AC dose (20% versus 5%), or the AC particle size. Without additional food supply, exposure to untreated and AC-amended sediments resulted in similar reduction of weight and lipid content, with no difference between ingestible and noningestible AC. Overall, whether with or without AC, the organisms showed signs of starvation, as the organisms would most likely rely on organic surface deposits for their diet in the environments from which the sediments were collected. When additional food was supplied, the organisms grew significantly and maintained higher lipid and glycogen contents. However, when feeding on fish food, organisms grew less in AC amendments with slightly lower lipid and glycogen contents relative to organisms exposed to untreated sediment. Batch tests show that AC did not sorb sediment-associated nitrogen but sorbed nitrogen from fish food. Despite some effects of AC on these deposit feeders, absolute effects of AC amendments on growth and energy reserves were not significant.     

Geochemistry of Cd,Cr, and Zn in highly contaminated sediments and its influences on assimilation by marine bivalves

We tested the controls of metal geochemistry in sediments collected from an extremely contaminated Chinese bay on metal assimilation by marine mussels and clams. Metal speciation in the contaminated sediments, quantified by the Tessier operational extraction method, was significantly dependent on metal concentrations in the sediments. The fractions of Cd in the easily exchangeable and carbonate phases increased, while the reducible and residue phases decreased with increasing Cd concentration. The majority (72-91%) of Cr was associated with the residue component with the remainder of Cr in the organic matter and reducible phases. Zn in carbonate phase increased, whereas in the organic matter and residue phases it decreased with increasing Zn concentration. The bioavailability of Cd, Cr, and Zn to marine green mussels (Perna viridis) and clams (Ruditapes philippinarum) was quantified using radiotracer spiked technique with concurrent measurements of speciation of spiked metals. There was a significant correlation between the Cd assimilation efficiency (AE) by both mussels and clams and Cd partitioning in the easily exchangeable and reducible phases. In contrast to previous studies, a negative correlation was found between the Cd AE and its total concentration in sediment, likely caused by the saturation of Cd binding sites in the gut or by its antagonistic interaction with a very high Zn concentration in these collected sediments. In contrast, there was no significant correlation between the AEs of Cr or Zn and any of their geochemical phases or their concentrations. The metal AEs were further quantified by experimentally manipulating different concentrations and ratios of acid volatile sulfide (AVS) and simultaneously extractable metals (SEM). There was no statistically significant relationship between the AEs of the three metals and the concentrations of AVS and SEM or [SEM-AVS]. Geochemical controls on metal assimilation from contaminated sediment are therefore only relatively apparent for Cd. The influences of metal speciation on metal bioavailability can be confounded by the degree to which sediments are contaminated with metals.     

Diffusion of the synthetic pyrethroid permethrin into bed-sediments

Bed-sediments are a sink for many micro-organic contaminants in aquatic environments. The impact of toxic contaminants on benthic fauna often depends on their spatial distribution, and the fate of the parent compounds and their metabolites. The distribution of a synthetic pyrethroid, permethrin, a compound known to be toxic to aquatic invertebrates, was studied using river bed-sediments in lotic flume channels. trans/cis-Permethrin diagnostic ratios were used to quantify the photoisomerization of the trans isomer in water. Rates were affected by the presence of sediment particles and colloids when compared to distilled water alone. Two experiments in dark/light conditions with replicate channels were undertaken using natural sediment, previously contaminated with permethrin, to examine the effect of the growth of an algal biofilm at the sediment-water interface on diffusive fluxes of permethrin into the sediment. After 42 days, the bulk water was removed, allowing a fine sectioning of the sediment bed (i.e., every mm down to 5 mm and then 5-10 mm, then every 10 mm down to 50 mm). Permethrin was detected in all cases down to a depth of 5-10 mm, in agreement with estimates by the Millington and Quirk model, and measurements of concentrations in pore water produced a distribution coefficient (Kd) for each section. High Kd's were observed for the top layers, mainly as a result of high organic matter and specific surface area. Concentrations in the algal biofilm measured at the end of the experiment under light conditions, and increases in concentration in the top 1 mm of the sediment, demonstrated that algal/ bacterial biofilm material was responsible for high Kd's at the sediment surface, and for the retardation of permethrin diffusion. This specific partition of permethrin to fine sediment particles and algae may enhance its threat to benthic invertebrates. In addition,the analysis of trans/cis-permethrin isomer ratios in sediment showed greater losses of trans-permethrin in the experiment under light conditions, which may have also resulted from enhanced biological activity at the sediment surface.     

Electrodialytic removal of Cu, Zn, Pb, and Cd from harbor sediment: influence of changing experimental conditions

Electrodialytic remediation (EDR) was used to remove Cu, Zn, Pb, and Cd from contaminated harbor sediment. Extraction experiments were made prior to EDR, and the metal desorption was pH dependent but not liquid-to-solid ratio (L/S) dependent. The desorption order was Cd > Zn > Pb > Cu. Electrodialytic experiments were made with HCl as desorbing agent in a sediment suspension, which was stirred during EDR. Effects of different current strengths and L/S ratios on the heavy metal removal were investigated on wet and air-dried sediment. The effects of drying the sediment were negligible for the removal of Cu, Zn, and Pb, probably due to oxidation of the sediments during stirring. Contrary, Cd removal was lower in the wet sediment as compared to the air-dried. The heavy metal removal was influenced by higher current strengths and varying L/S ratios. The highest removal obtained was in an experiment with dry sediment (L/S 8) and a 70 mA applied current that lasted 14 days. These experimental conditions were thereafter used to remediate more strongly contaminated sediments. Regardless of the initial heavy metal concentrations in the sediments, 67-87% Cu, 79-98% Cd, 90-97% Zn, and 91-96% Pb were removed.     

Release and phase partitioning of metals from anoxic estuarine sediments during periods of simulated resuspension

Periodically, marine sediments are subjected to physical processes which resuspend them into the water column, releasing previously sequestered metals. The role of resuspension energy and duration on release and subsequent redistribution of sediment bound metals was measured experimentally using a particle entrainment simulator. Two metal contaminated anoxic sediments with different physical and chemical characteristics were resuspended for 12 h at energies of 2 and 5 dynes cm(-2). Samples were taken at specified intervals, and the water column pH, Eh and dissolved oxygen levels were monitored continuously. Over time, metal concentrations increased in the particulate (nonfilterable > or = 1 microm) and filterable (< 1 microm) phases of the overlying water. In general, metal enrichment followed the Irving-Williams order of complex stability. Overall, the sediment's chemical and physical composition were major factors in determining the amount of metal released, more so than the level of resuspension energy applied. These results provide insight into how physical and chemical processes interact during sediment resuspension to release sediment bound metals and control their phase distribution in the water column.     

Dynamic model for the accumulation of cadmium and zinc from water and sediment by the aquatic oligochaete, Tubifex tubifex

In aquatic environments, organisms are exposed to and accumulate metals via waterborne and dietary routes including ingested sediment. A key element in understanding metal uptake and accumulation is information concerning the relative importance of the routes of uptake and the kinetics of the processes. In this work the bioaccumulation of the essential element zinc and the nonessential element cadmium were studied from the aqueous and sediment phase, in the cosmopolitan oligochaete Tubifex tubifex, using the radiotracers 109Cd and 65Zn. A compartmental kinetic model was constructed and parametrized by fitting the model to metal body concentrations. Using the pharmacokinetic modeling approach and taking into account the distribution of the metal between water and sediment, the different routes were quantitatively separated. Under the experimental conditions, the sediment phase accounted for 9.8% of the cadmium and 52% of the zinc uptake. These values are based on the uptake of the radiotracers spiked sediments and therefore likely represent maximal values since it was shown that under the specific conditions this was the most mobile metal fraction. This difference was largely explained by the large difference in assimilation efficiency between cadmium and zinc. Simulations of different conditions showed that both dissolved and sediment-associated metal can be important sources of metal exposure for the worms and that the relative importance strongly depends on the metal and exposure conditions including the lability of the metals in the sediment phase.     

Historical trends in mercury sedimentation and mixing in the Strait of Georgia, Canada

Seventeen sediment cores collected in the Strait of Georgia reveal a history of mercury contamination that began in the 1860s and include episodic contamination during World War II and in the late 1960s. Surface sediment mercury concentrations ranged from 60 to 420 ng/g dry weight and the current fluxes to sediments are estimated at 5-181 ng cm(-2) a(-1). In one location in Port Moody Arm, a Hg spill seems to have sufficiently poisoned the sediments to eliminate biomixing for about 20 years. Although the surface concentration of Hg is likely to decrease at all stations in coming years, sites in the industrialized Vancouver Harbor and Port Moody Arm will continue to be sufficiently contaminated to endanger benthic organisms. Variations in sedimentation and mixing rates among sites result in surface sediment Hg concentration patterns that do not reflect accurately the distribution of Hg flux. In particular, the concentration of Hg in sediments near the mouth of the Fraser River is low, despite the high Hg load of that river, because of dilution by other particles. A preliminary Hg budget indicates that most of the Hg enters the Strait of Georgia via the Fraser River (2090 kg a(-1)), and that, while burial in Strait of Georgia sediments is a major sink (1800 kg a(-1)), there may be a significant outflow of Hg through Juan de Fuca Strait (approximately 3400 kg a(-1)).     

Mobilization, adsorption, and bioavailability of Pt and Pd in coastal sediments: the role of the polychaete, Arenicola marina

The biogeochemical behavior of Pt and Pd in coastal sediments has been examined in a series of microcosms, both in the presence and absence of the deposit-feeding invertebrate, Arenicola marina. When metals were introduced to the overlying water column as solutes from acidified standards, A. marina dramatically enhanced their sorption to sediment throughout the core depth (14 cm) compared with an unfaunated control by exposing a greater surface area of particles to more rapidly ventilating contaminated water. After a 10 day incubation period, the assimilation efficiency (AE) by A. marina was about 10% for Pt and 1% for Pd. Calculations based on either partition constants or operational measures of metal bioaccessibility in sediment (using the protein, BSA) suggested that both aqueous and dietary sources of metal were important When Pt and Pd were introduced to the sediment-water interface as components of ground catalytic converter particles, significant subduction was effected by A. marina, and metals were solubilized to a greater extent than in an unfaunated control. AE in these experiments was < 0.1% for Pt and about 1% for Pd, and the most important vector for assimilation appeared to be from the aqueous phase via partial solubilization of metal from catalytic material. The findings of this study improve our understanding of the availability, cycling, and fate of Pt and Pd in contaminated estuaries and coastal waters.     

Bioaccumulation of perfluorochemicals in sediments by the aquatic oligochaete Lumbriculus variegatus

Bioaccumulation of perfluoroalkyl sulfonates, perfluorocarboxylates, and 2-(N-ethylperfluorooctane sulfonamido) acetic acid (N-EtFOSAA) from laboratory-spiked and contaminated field sediments was assessed using the freshwater oligochaete, Lumbriculus variegatus. Semistatic batch experiments were conducted to monitor the biological uptake of these perfluorochemicals (PFCs) over 56 days. The elimination of PFCs was measured as the loss of PFCs in L. variegatus exposed to PFC-spiked sediment for 28 days and then transferred to clean sediment. The resultant data suggest that PFCs in sediments are readily bioavailable and that bioaccumulation from sediments does not continually increase with increasing perfluorocarbon chain length. Perfluorooctane sulfonate (PFOS) and perfluorononanoate were the most bioaccumulative PFCs, as measured by laboratory-based estimated steady-state biota sediment accumulation factors (BSAFs) and BSAFs measured using contaminated field sediments. Elimination rate constants for perfluoroalkyl sulfonates and perfluorocaroboxylates were generally smaller than those previously measured for other organic contaminants. Last, a PFOS precursor, N-EtFOSAA, accumulated in the worm tissues and appeared to undergo biotransformation to PFOS and other PFOS precursors. This suggests that N-EtFOSAA, which has been detected in sediments and sludge often at levels exceeding PFOS, may contribute to the bioaccumulation of PFOS in aquatic organisms.     

Accumulation of copper and zinc in periphyton in response to dynamic variations of metal speciation in freshwater

Although the free ion activity model (FIAM) has been well-established in laboratory studies, there remains the need for field data in order to validate the applicability of this model in natural systems. The objective of this study was to investigate the response of copper and zinc accumulation in periphyton to short-term variations in metal concentration and speciation in freshwater. During heavy rain events, dissolved Cu in the Furtbach stream increased from 40 to 118 nM, while dissolved Zn increased from 45 to 147 nM due to the release of metals from contaminated sediments. Increases in free copper and free zinc ions in the water (from 10(-14) to 10(-11.5) M for Cu2+; from 1 to 15 nM for Zn2+) were observed during the onset of heavy rain events. Periphytic algae collected from artificial substrates had an intracellular copper content (0.2-2.8 micromol/g dry weight (dw)) that varied as a function of the exchangeable copper in the water (labile form) rather than the free Cu2+. Intracellular zinc content (1.5-8.0 micromol/g dw) was found to follow the same trend as the free zinc ion concentration. Adsorbed Cu and Zn on periphyton showed a very dynamic response to variations in dissolved metal concentration. Different concentrations of dissolved manganese during the two time periods may affect the accumulation of zinc and copper by competition for metal uptake.