Long-term monitoring and modeling of PAHs in capped sediments at the Grand Calumet River.

The assessment of a cap for remediation of sediments requires long-term monitoring because of the slow migration of contaminants in porous media. In this study, coring and passive sampling tools were used to assess the transport and degradation of polycyclic aromatic hydrocarbons (PAHs) in an amended cap (sand + Organoclay® PM-199) in the Grand Calumet River (Indiana, USA) during four sampling events from 2012 to 2019. Measurements of three PAHs (phenanthrene (Phe), pyrene (Pyr) and benzo[a]pyrene (BaP), representing low, medium, and high molecular weight compounds, respectively) showed a difference of at least two orders of magnitude between bulk concentrations in the native sediments and the remediation cap. Averages of pore water measurements also showed lower levels in the cap respective to the native sediments by a factor of at least 7 for Phe and 3 for Pyr. In addition, between the baseline (BL), which corresponds to observations from 2012 to 2014, and the measurements in 2019, there was a decrease in depth-averaged pore water concentrations of Phe (C2019/CBL=0.20-0.07+0.12 in sediments and 0.27-0.10+0.15 in cap) and Pyr (C2019/CBL=0.47-0.12+0.16 in sediments and 0.71-0.20+0.28 in the cap). In the case of BaP in pore water, no change was observed in native sediments (C2019/CBL=1.0-0.24+0.32) and there was an increase in the cap (C2019/CBL=2.0-0.54+0.72). Inorganic anions and estimates of pore water velocity along with measurements of PAHs were used to model the fate and transport of contaminants. The modeling suggested that degradation of Phe (t1/2=1.12-0.11+0.16 years) and Pyr (t1/2=5.34-1.8+5.3 years) in the cap is faster than migration, thus the cap is expected to be protective of the sediment-water interface indefinitely for these constituents. No degradation was noted in BaP and the contaminant is expected to reach equilibrium in the capping layer over approximately 100 years if there exists sufficient mass of BaP in the sediments and there is no deposition of clean sediment at the surface.

Interlaboratory Study of Polyethylene and Polydimethylsiloxane Polymeric Samplers for Ex Situ Measurement of Freely Dissolved Hydrophobic Organic Compounds in Sediment Porewater.

We evaluated the precision and accuracy of multilaboratory measurements for determining freely dissolved concentrations (Cfree ) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in sediment porewater using polydimethylsiloxane (PDMS) and low-density polyethylene (LDPE) polymeric samplers. Four laboratories exposed performance reference compound (PRC) preloaded polymers to actively mixed and static ex situ sediment for approximately 1 month; two laboratories had longer exposures (2 and 3 months). For Cfree results, intralaboratory precision was high for single compounds (coefficient of variation 50% or less), and for most PAHs and PCBs interlaboratory variability was low (magnitude of difference was a factor of 2 or less) across polymers and exposure methods. Variability was higher for the most hydrophobic PAHs and PCBs, which were present at low concentrations and required larger PRC-based corrections, and also for naphthalene, likely due to differential volatilization losses between laboratories. Overall, intra- and interlaboratory variability between methods (PDMS vs. LDPE, actively mixed vs. static exposures) was low. The results that showed Cfree polymer equilibrium was achieved in approximately 1 month during active exposures, suggesting that the use of PRCs may be avoided for ex situ analysis using comparable active exposure; however, such ex situ testing may not reflect field conditions. Polymer-derived Cfree concentrations for most PCBs and PAHs were on average within a factor of 2 compared with concentrations in isolated porewater, which were directly measured by one laboratory; difference factors of up to 6 were observed for naphthalene and the most hydrophobic PAHs and PCBs. The Cfree results were similar for academic and private sector laboratories. The accuracy and precision that we demonstrate for determination of Cfree using polymer sampling are anticipated to increase regulatory acceptance and confidence in use of the method. Environ Toxicol Chem 2022;41:1885-1902. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Application of polyoxymethylene passive air sampler to monitor hydrophobic organics in air around a confined disposal facility.

Volatile losses of hydrophobic organic contaminants from a confined disposal facility (CDF) containing dredged contaminated sediments is of substantial concern to surrounding communities. A partitioning passive sampling approach using polyoxymethylene (POM) was applied to measure long-term average (weeks to months) air concentrations resulting from evaporation at a CDF. Measurements at 10 locations surrounding the CDF using the POM air samplers indicated that the highest concentrations of ΣPCBs∼13 ng/m3 and ΣPAHs ∼65 ng/m3 were measured during an active dredge material placement period when the average temperature was 23 °C. The measurements were dominated by the more volatile, lower molecular weight compounds of each type. Partitioning to the POM during the post dredge material placement period with average temperature of 5 °C was corrected for temperature and the measured ∑PCBs and ∑PAHs were ∼3 ng/m3 and 45 ng/m3 respectively. The partitioning passive sampling measurements agreed well with the available weekly 24-h high-volume air samples (HVAS) averaged over the POM equilibration time for lower congener number PCBs (15, 18, 20/28 and 31) and naphthalene but were as much as 10 times lower than HVAS for high molecular weight PAHs. The difference was likely the result of the greater association of these PAHs with particulates and sources other than evaporation from the CDF. The POM air sampler achieved the goal of providing a long-term average air concentration without having to collect, analyze and average multiple HVAS samples although the technique is largely limited to the lower molecular weight PAHs and PCBs and different equilibration times for different compounds complicate its use and analysis.

Powdered activated carbon (PAC) amendment enhances naphthalene biodegradation under strictly sulfate-reducing conditions.

Capping represents an efficient and well-established practice to contain polycyclic aromatic hydrocarbons (PAHs) in sediments, reduce mobility, and minimize risks. Exposure to PAHs can encourage biodegradation, which can improve the performance of capping. This study investigates biodegradation of naphthalene (a model PAH) in highly reducing, sediment-like environments with amendment of different capping materials (PAC and sand). Microcosms were prepared with sediment enrichments, sulfate as an electron acceptor, and naphthalene. Results show that PAC stimulates naphthalene biodegradation and mineralization, as indicated by production of 14CO2 from radiolabeled naphthalene. Mineralization in PAC systems correlates with the enrichment of genera (Geobacter and Desulfovirga) previously identified to biodegrade naphthalene (Spearman's, p < 0.05). Naphthalene decay in sand and media-free systems was not linked to biodegradation activity (ANOVA, p > 0.05), and microbial communities were correlated to biomass yields rather than metabolites. Naphthalene decay in PAC systems consists of three stages with respect to time: latent (0-88 days), exponential decay (88-210 days), and inactive (210-480 days). This study shows that PAC amendment enhances naphthalene biodegradation under strictly sulfate-reducing conditions and provides a kinetic and metagenomic characterization of systems demonstrating naphthalene decay.

Assessing Biota Accumulation Due to Contamination of Sediments by Storm Water Heavy Metals.

Evaluating sediment recontamination due to storm water discharges is important when evaluating the long-term effectiveness of sediment remediation efforts at reducing biological impacts. The bioaccumulation of the heavy metals zinc, nickel, copper, cadmium, mercury, and lead and the metalloid arsenic in a clam (Macoma nasuta) was studied in surficial sediments before and after storm water inputs from Paleta Creek, California, USA, during wet seasons in 2015 to 2016 and 2016 to 2017. The bioaccumulation was compared with bulk sediment concentrations and porewater concentrations measured by diffusion gradient in thin film devices. Significant reductions in biota accumulation and porewater concentrations were observed in samples collected after storm seasons compared with before storm seasons despite bulk sediment concentrations remaining the same or increasing. This was apparently the result of the deposition of storm water contaminants in low bioavailable forms. The bioaccumulation of all the measured contaminants showed a positive significant correlation with porewater concentrations (p < 0.1, α = 0.1) and weak or no correlations with bulk sediment concentration. In conclusion, observed bulk sediment recontamination due to storm water should not be assumed to lead directly to greater biota accumulation without bioavailability assessment. Environ Toxicol Chem 2020;39:2475-2484. © 2020 SETAC.

Bioavailability assessment in activated carbon treated coastal sediment with in situ and ex situ porewater measurements.

Passive sampling and bioaccumulation assessments were used to evaluate the performance of activated carbon (AC) remediation of polychlorinated biphenyl (PCB) contaminated sediment offshore in Parcel F of the former Hunters Point Naval Shipyard (HPNS) (San Francisco, California). Two different composite AC materials, AquaGate+PAC™ (86 tons) and SediMite™ (24 tons) were placed on the sediment surface covering an area of 3200 m2. PCB tissue concentrations in the clam Macoma nasuta were reduced 75 to 80% in pilot amendment areas after 8 months and 84-87% in non-lipid normalized tissues after 14 months during in situ monitoring, confirming the effectiveness of the AC at reducing bioavailability of the PCBs. Polydimethylsiloxane (PDMS) passive samplers were applied to evaluate and monitor freely dissolved concentrations (Cfree) of PCBs in sediment porewater before AC placement (i.e., during baseline) and at 8 months, 14 months and 26 months following placement. Although AC composite materials were placed only at the surface, 80% reductions were observed to a depth of 16 cm after 8 months and up to 26 cm after 26 months in AquaGate+PAC treatment area. Total PCB porewater concentrations in surface sediments (1-6 cm) were reduced 89 and 91% in the AquaGate+PAC and SediMite areas during final sampling. Ex situ passive sampling showed porewater concentrations 2-5 times larger than in situ measurements due to the absence of hyporheic exchange in laboratory measurements and near equilibration between sediment and porewater. Estimated post placement ex situ porewater concentrations were more consistent with a model of bioaccumulation using the octanol-water partition coefficient (KOW) as a bioaccumulation factor leading to a hypothesis that the bioaccumulation factor in the deposit feeding clam is better estimated by equilibrium ex situ porewater measurements.

Assessing sediment recontamination from metals in stormwater.

Recontamination of sediments by stormwater is a major concern when evaluating the potential effectiveness of sediment remediation. Stormwater and sediment sampling were conducted in a mixed-use watershed at Paleta Creek in San Diego, CA to evaluate methods for assessing sediment recontamination by metals. Size-segregated stormwater contaminant loads with simultaneous receiving water and sediment measurements were used to identify dominant sources and contaminants with respect to their impact on sediment recontamination. Most of the stormwater contaminant loads of Cd, Cu, Pb, and Zn were associated with residential and highway sources from the upstream portions of the watershed and As, Ni and Hg were more significantly influenced by the downstream area of the watershed. Cd was strongly associated with large particles (>63 µm) and observed to settle in near shore areas with some attenuation due to mixing and dilution. Cu, in contrast, was associated more with the filtered fraction (<0.45 µm) and clay fraction (0.45-5 µm), resulting in less near shore sediment recontamination. Depositing sediment and other metals, particularly Cu and Hg, exhibited greater accumulation in settling traps than could be attributed to stormwater loads indicating the importance of other sources or resuspension of bay sediments on surficial sediment concentrations. Pb, Zn, Ni, and As showed influences of both stormwater and other sources. The study showed that measurement of size-segregated stormwater contaminant mass and concentrations combined with simultaneous measurements of deposition in sediment traps could differentiate between recontamination by stormwater and that of other sources.

Development of polyoxymethylene passive sampler for assessing air concentrations of PCBs at a confined disposal facility (CDF).

In this study, 76 µm polyoxymethylene (POM) strips were evaluated as a passive air sampler (PAS) for monitoring the volatile emissions from dredged material placed in confined disposal facilities (CDF). Laboratory evaluations were used to assess the uptake kinetics, average equilibrium time, and estimate the POM-air partition coefficients (KPOM-A) of 16 PCB congeners. The uptake kinetics defined the effective averaging time for air sampling and ranged from about a week for dichlorobiphenyls to 2 weeks or more for tetra- and pentachlorobiphenyls at ∼20 °C under internal mass transfer resistance control which was applicable for Log KPOM-A < 8. The measured Log KPOM-A for PCBs ranged from 5.65 to 9.34 and exhibited an average deviation of 0.19 log unit from the theoretical value of KPOM-W/KAW. The PAS approach was then tested with a preliminary field application (n = 17) at a CDF allowing equilibration over 42 days. The field application focused on lower congener PCBs as a result of the estimated increase in KPOM-A and longer uptake times expected at the low ambient temperatures during the field study (average of 3.5 °C). Total PCB air concentrations around the CDF averaged 0.32 ng/m3 and varied according to proximity to placement of the dredged materials and predominant wind directions. Average PAS concentration of low congener number PCBs (15, 18, 20/28, 31) were compared to available high volume air sampler (HVAS) measurements. The PAS concentrations were within 20% of HVAS in the dominant north and south directions and showed similar trends as east and west HVAS samplers although PAS concentrations were as much as an order of magnitude below the west HVAS.

Seasonal Toxicity Observed with Amphipods (Eohaustorius estuarius) at Paleta Creek, San Diego Bay, USA.

To assess potential impacts on receiving systems, associated with storm water contaminants, laboratory 10-d amphipod (Eohaustorius estuarius) survival toxicity tests were performed using intact sediment cores collected from Paleta Creek (San Diego Bay, CA, USA) on 5 occasions between 2015 and 2017. The approach included deposition-associated sediment particles collected from sediment traps placed at each of 4 locations during the 2015 to 2016 wet seasons. The bioassays demonstrated wet season toxicity, especially closest to the creek mouth, and greater mortality associated with particles deposited in the wet season compared with dry season samples. Grain size analysis of sediment trap material indicated coarser sediment at the mouth of the creek and finer sediment in the outer depositional areas. Contaminant concentrations of metals (Cd, Cu, Hg, Ni, Pb, and Zn) and organic compounds (polycyclic aromatic hydrocarbons [PAHs], polychlorinated biphenyls [PCBs], and pesticides) were quantified to assess possible causes of toxicity. Contaminant concentrations were determined in the top 5 cm of sediment and porewater (using passive samplers). Whereas metals, PAHs, and PCBs were rarely detected at sufficient concentrations to elicit a response, pyrethroid pesticides were highly correlated with amphipod toxicity. Summing individual pyrethroid constituents using a toxic unit approach suggested that toxicity to E. estuarius could be associated with pyrethroids. This unique test design allowed delineation of spatial and temporal differences in toxicity, suggesting that storm water discharge from Paleta Creek may be the source of seasonal toxicity. Environ Toxicol Chem 2019;39:229-239. © 2019 SETAC.

Combined Effects of Plant Cultivation and Sorbing Carbon Amendments on Freely Dissolved PAHs in Contaminated Soil.

We report freely dissolved concentrations ( Cfree) of PAHs in soils amended with 2.5% biochar and activated carbon (AC) during a long-term (18-months) field experiment. The study evaluates also the impact of different plants (clover, grass, willow) on Cfree PAHs. The cumulative effect of treatments on nitrogen and available forms of phosphorus, potassium, and magnesium is also assessed. The direct addition of biochar to soil did not cause any immediate reduction of the sum of 16 Cfree PAHs, while AC resulted in a slight reduction of 5- and 6 ring compounds. The efficiency of binding of Cfree PAHs by biochar and AC increased with time. For biochar, the maximum reduction of 4-6-ring PAHs (18-67%) was achieved within 6 months. For 2- and 3-ring PAHs, a gradual decrease of Cfree was observed which reached 60-66% at 18 months. AC proved to be better in reducing Cfree PAHs than biochar, though for 2- and 3-ring PAHs, the differences in AC and biochar performances were smaller than those for 4-6-ring PAHs. After 18 months, a significantly lower content of Cfree PAHs was observed in the soil with plants compared to the unplanted soil. Except for potassium, AC or biochar did not negatively impact nutrient availability.

Bioaccessibility of polycyclic aromatic hydrocarbons in activated carbon or biochar amended vegetated (Salix viminalis) soil.

The aim of the present study was to determine the effect of activated carbon (AC) or biochars on the bioaccessibility (Cbioacc) of polycyclic aromatic hydrocarbons (PAHs) in soils vegetated with willow (Salix viminalis). The study determined the effect of willow on the Cbioacc PAHs and the effect of the investigated amendments on changes in dissolved organic carbon (DOC), crop yield and the content of PAHs in plants. PAH-contaminated soil was amended with 2.5 wt% AC or biochar. Samples from individual plots with and without plants were collected at the beginning of the experiment and after 3, 6, 12 and 18 months. The Cbioacc PAHs were determined using sorptive bioaccessibility extraction (SBE) (silicon rods and hydroxypropyl-ß-cyclodextrin). Both AC and biochar caused a decrease in the Cbioacc PAHs. Immediately after adding AC, straw-derived biochar or willow-derived biochar to the soil, the reduction in the sum of 16 (Σ16) Cbioacc PAHs was 70.3, 38.0, and 29.3%, respectively. The highest reduction of Cbioacc was observed for 5- and 6-ring PAHs (from 54.4 to 100%), whereas 2-ring PAHs were reduced only 8.0-25.4%. The reduction of Cbioacc PAHs increased over time. Plants reduced Cbioacc in all soils although effects varied by soil treatment and PAH. Willow grown in AC- and biochar-amended soil accumulated less phenanthrene than in the control soil. The presence of AC in the soil also affected willow yield and shoot length and DOC was reduced from 53.5 to 66.9% relative to unamended soils. In the biochars-amended soil, no changes in soil DOC content were noted nor effects on willow shoot length.

Long-term PAH monitoring results from the Anacostia River active capping demonstration using polydimethylsiloxane (PDMS) fibers.

In this paper, the long-term monitoring results for hydrophobic organic compounds, specifically polycyclic aromatic hydrocarbons (PAHs), from a field demonstration of capping contaminated sediments at the Anacostia River in Washington DC are presented and analyzed. In situ pore water concentrations in field-contaminated sediments in the demonstration caps were quantified using a polydimethylsiloxane (PDMS)-based passive sampling device. High resolution vertical pore water concentration profiles were measured using the device and were used to infer fate and transport of polycyclic aromatics hydrocarbons (PAHs) at the site. The derived pore water concentrations were compared with observed bioaccumulation and solid-phase concentration profiles to infer contaminant migration rates and mechanisms. Observed pore water concentrations were found to be a better predictor of bioaccumulation than solid-phase concentrations. Solid-phase concentrations were low in cores which implied containment of contamination; however pore water profiles showed that contaminant migration had occurred in the first few years after cap placement. The discrepancy is the result of the low sorption capacity of the sand. Because of surface re-contamination, low sorption capacity in the demonstration caps and strong tidal pumping effects, steady state contaminant profiles were reached in the caps several years after placement. Despite re-contamination at the surface, steady state concentrations in the capped areas showed decreased contamination levels relative to the control area.

Assessment of potential anaerobic biotransformation of organic pollutants in sediment caps.

In situ capping is a remedial approach for reducing the risk of biota exposure to sediment contaminants. Biotransformation of contaminants in sand-based sediment caps, rarely considered in sediment cap design, could further reduce the exposure risk. The anaerobic biotransformation of benzene, toluene, ethylbenzene, xylenes (BTEX), monochlorobenzene, dichlorobenzenes and naphthalene was evaluated with sediments from Onondaga Lake in dilute sediment slurries and in sand-capped sediment laboratory-scale columns. The percentage of sediment samples demonstrating biotransformation under anaerobic conditions in slurries incubated at 12°C was greatest for BTEX, followed by monochlorobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene and 1,3-dichlorobenzene. Only toluene biotransformation was observed in sand cap columns. The rate of toluene biotransformation diminished over time, which might be due to inhibition caused by hydrogen from the experimental setup. Results suggest potential for the biotransformation of toluene, and possibly other pollutants, in sand-based sediment caps under anaerobic conditions at low temperatures.

Effect of applied voltage, initial concentration, and natural organic matter on sequential reduction/oxidation of nitrobenzene by graphite electrodes.

Carbon electrodes are proposed in reactive sediment caps for in situ treatment of contaminants. The electrodes produce reducing conditions and H(2) at the cathode and oxidizing conditions and O(2) at the anode. Emplaced perpendicular to seepage flow, the electrodes provide the opportunity for sequential reduction and oxidation of contaminants. The objectives of this study are to demonstrate degradation of nitrobenzene (NB) as a probe compound for sequential electrochemical reduction and oxidation, and to determine the effect of applied voltage, initial concentration, and natural organic matter on the degradation rate. In H-cell reactors with graphite electrodes and buffer solution, NB was reduced stoichiometrically to aniline (AN) at the cathode with nitrosobenzene (NSB) as the intermediate. AN was then removed at the anode, faster than the reduction step. No common AN oxidation intermediate was detected in the system. Both the first order reduction rate constants of NB (k(NB)) and NSB (k(NSB)) increased with applied voltage between 2 V and 3.5 V (when the initial NB concentration was 100 µM, k(NB) = 0.3 h(-1) and k(NSB) = 0.04 h(-1) at 2 V; k(NB) = 1.6 h(-1) and k(NSB) = 0.64 h(-1) at 3.5 V) but stopped increasing beyond the threshold of 3.5 V. When initial NB concentration decreased from 100 to 5 µM, k(NB) and k(NSB) became 9 and 5 times faster, respectively, suggesting that competition for active sites on the electrode surface is an important factor in NB degradation. Presence of natural organic matter (in forms of either humic acid or Anacostia River sediment porewater) decreased k(NB) while slightly increased k(NSB), but only to a limited extent (∼factor of 3) for dissolved organic carbon content up to 100 mg/L. These findings suggest that electrode-based reactive sediment capping via sequential reduction/oxidation is a potentially robust and tunable technology for in situ contaminants degradation.

PAH degradation and redox control in an electrode enhanced sediment cap.

Capping is typically used to control contaminant release from the underlying sediments. However, the presence of conventional sediment caps will often eliminate or slow natural degradation that might otherwise occur at the surface sediment. The objective of this study was to explore the potential of a novel reactive capping, an electrode enhanced cap for the remediation of PAH contaminated sediment. The study on electrode enhanced biodegradation of PAH in slurries showed that naphthalene concentration decreased from ~1000 µg/L to ~50 µg/L, and phenanthrene decreased from ~150 µg/L to ~30 µg/L in ElectroBioReactor within 4 days, and the copy numbers of PAH degrading genes increased by almost 2 orders of magnitude. In a cap microcosm, two carbon electrodes were emplaced within a sediment cap with an applied potential of 2 V. The anode was placed at the sediment-cap interface encouraging oxidizing conditions. Oxidation and Reduction Potential (ORP) profiles showed redox potential approximately 60-100 mV higher at the sediment-cap interface with the application of voltage than in controls. Vertical profiles of phenanthrene porewater concentration were obtained by PDMS-coated fiber, and results showed that phenanthrene at the depth of 0-0.5 cm below the anode was degraded to ~70% of the initial concentration within 10 weeks. PAH degrading genes showed an increase of approximately 1 order of magnitude at the same depth. The no power controls showed no degradation of PAH. These findings suggest that electrode enhanced capping can be used to control redox potential, provide microbial electron acceptor, and stimulate PAH degradation.

A sediment ecotoxicity assessment platform for in situ measures of chemistry, bioaccumulation and toxicity. Part 1: System description and proof of concept.

In situ-based testing using aquatic organisms has been widely reported, but is often limited in scope and practical usefulness in making decisions on ecological risk and remediation. To provide this capability, an integrated deployment system, the Sediment Ecotoxicity Assessment (SEA) Ring was developed, which incorporates rapid in situ hydrological, chemical, bioaccumulation, and toxicological Lines-of-Evidence (LoE) for assessing sediment and overlying water contamination. The SEA Ring system allows for diver-assisted, or diverless, deployment of multiple species of ecologically relevant and indigenous organisms in three different exposures (overlying water, sediment-water interface, and bulk sediment) for periods ranging from two days to three weeks, in a range of water systems. Measured endpoints were both sublethal and lethal effects as well as bioaccumulation. In addition, integrated passive sampling devices for detecting nonpolar organics (solid phase micro-extraction fibers) and metals (diffusive gradients in thin films) provided gradient measures in overlying waters and surficial sediments.

A sediment ecotoxicity assessment platform for in situ measures of chemistry, bioaccumulation and toxicity. Part 2: Integrated application to a shallow estuary.

A comprehensive, weight-of-evidence based ecological risk assessment approach integrating laboratory and in situ bioaccumulation and toxicity testing, passive sampler devices, hydrological characterization tools, continuous water quality sensing, and multi-phase chemical analyses was evaluated. The test site used to demonstrate the approach was a shallow estuarine wetland where groundwater seepage and elevated organic and inorganic contaminants were of potential concern. Although groundwater was discharging into the surficial sediments, little to no chemical contamination was associated with the infiltrating groundwater. Results from bulk chemistry analysis, toxicity testing, and bioaccumulation, however, suggested possible PAH toxicity at one station, which might have been enhanced by UV photoactivation, explaining the differences between in situ and laboratory amphipod survival. Concurrently deployed PAH bioaccumulation on solid-phase micro-extraction fibers positively correlated (r(2) ≥ 0.977) with in situ PAH bioaccumulation in amphipods, attesting to their utility as biomimetics, and contributing to the overall improved linkage between exposure and effects demonstrated by this approach.

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).

Effects of cyclic changes in pH and salinity on metals release from sediments.

The effects of dynamic changes in pH and salinity on metal speciation and release are investigated with sediments posed in a simulated estuarine environment. The release of Zn, Cd, Mn, and Fe was studied using sediment from the Anacostia River (Washington, DC, USA) spiked with freshly precipitated amorphous cadmium sulfide to increase Cd content. The sediment was exposed to salt water (high pH, ionic strength) and freshwater (neutral pH, minimal ionic strength) continuously and alternately (to mimic tidal changes) in small microcosms over 100 d. At the conclusion of the experiments, the vertical profiles of acid volatile sulfide (AVS) and simultaneously extracted metals (SEM) as well as porewater metals and anion concentrations were characterized. Acid volatile sulfide oxidation at the sediment surface led to a commensurate increase in dissolved metal species and metal release that was strongly dependent on the changes in the overlying water characteristics. Total Cd release was substantially higher during exposure to salt water, although, as a result of complexation, predicted dissolved Cd(2+) concentration in the overlying water was higher during exposure to freshwater. Total Zn release was little changed during exposure to salt water and freshwater, although the predicted dissolved Zn(2+) concentration was much higher during freshwater exposures. No significant iron was released because of the rapid oxidation of ferrous iron (Fe(2+)) in aerobic surficial sediments and overlying water. The present study suggests that cyclic changes in pH and salinity in the overlying water can dramatically influence metal release from estuarine sediments.