Yongju Choi

Passive sampling methods for contaminated sediments: Practical guidance for selection, calibration, and implementation

This article provides practical guidance on the use of passive sampling methods (PSMs) that target the freely dissolved concentration (Cfree) for improved exposure assessment of hydrophobic organic chemicals in sediments. Primary considerations for selecting a PSM for a specific application include clear delineation of measurement goals for Cfree, whether laboratory-based “ex situ” and/or field-based “in situ” application is desired, and ultimately which PSM is best-suited to fulfill the measurement objectives. Guidelines for proper calibration and validation of PSMs, including use of provisional values for polymer–water partition coefficients, determination of equilibrium status, and confirmation of nondepletive measurement conditions are defined. A hypothetical example is described to illustrate how the measurement of Cfree afforded by PSMs reduces uncertainty in assessing narcotic toxicity for sediments contaminated with polycyclic aromatic hydrocarbons. The article concludes with a discussion of future research that will improve the quality and robustness of Cfree measurements using PSMs, providing a sound scientific basis to support risk assessment and contaminated sediment management decisions. Integr Environ Assess Manag 2014;10:210–223.

Long-term monitoring and modeling of the mass transfer of polychlorinated biphenyls in sediment following pilot-scale in-situ amendment with activated carbon.

The results of five years of post-treatment monitoring following in-situ activated carbon (AC) placement for stabilization of polychlorinated biphenyls (PCBs) at an inter-tidal mudflat adjacent to Hunters Point Shipyard, San Francisco Bay, CA, USA are reported in this paper. After five years, AC levels of the sediment cores were comparable to those at earlier sampling times. Passive sampler uptake validated the benefit of the AC amendment with a strong local sorbent dose-response relationship. The PCB uptakes in passive samplers decreased up to 73% with a 3.7 dry wt.% AC dose after five years, confirming the temporal enhancement of the amendment benefit from a 19% reduction with a 4.4% dose observed within one month. The long-term effectiveness of AC, the local AC dose response, the impact of fouling by NOM, the spatial heterogeneity of AC incorporation, and the effects of advective sediment pore-water movement are discussed with the aid of a PCB mass transfer model. Modeling and experimental results indicated that the homogeneous incorporation of AC in the sediment will significantly accelerate the benefit of the treatment.

Measurement and Modeling of Activated Carbon Performance for the Sequestration of Parent- and Alkylated-Polycyclic Aromatic Hydrocarbons in Petroleum-Impacted Sediments

We present a first comprehensive set of experiments that demonstrate the performance of activated carbon (AC) to reduce the availability of polycyclic aromatic hydrocarbons (PAHs) including alkylated-PAHs in petroleum-impacted sediments. The uptake in polyethylene samplers for total PAHs in a well-mixed sediment slurry was reduced up to 99% and 98% for petroleum-impacted sediments with oil contents of 1% and 2%, respectively, by treatment with 5% AC. The AC showed similar efficiency for parent-PAHs and a suite of alkylated-PAHs, which predominate over parent-PAHs in petroleum-impacted sediments. A mass transfer model was used to simulate the AC performance in a slurry phase with site-specific mass transfer parameters determined in this study. Comparison between the experimental data and simulation results suggested that dissolved organic matter and/or oil phase may have attenuated the AC performance by a factor of 5-6 for 75-300 μm AC with 5% dose at one month. The attenuation in AC performance became negligible with increase in AC-sediment slurry contact time to 12 months and with decrease in AC particle size. The results show the potential for AC amendment to sequester PAHs in petroleum-impacted sediments and the effect of contact time and AC particle size on the efficiency of the treatment.

Polyethylene-water partitioning coefficients for parent- and alkylated-polycyclic aromatic hydrocarbons and polychlorinated biphenyls.

We report polyethylene (PE)-water partitioning coefficients (K(PE)) for 17 parent-polycyclic aromatic hydrocarbons (PAHs), 22 alkylated-PAHs, 3 perdeuterated parent-PAHs, and 100 polychlorinated biphenyl (PCB) congeners or coeluting congener groups. The K(PE) values for compounds in the same homologue group are within 0.2 log units for alkylated-PAHs but span up to an order of magnitude for PCBs, due to the greater contribution of the position of the substituents (i.e., chlorines for PCBs and alkyl groups for alkylated-PAHs) to the molecular structure. The K(PE) values in deionized water for parent- and alkylated-PAHs show a good correlation with a regression model employing the number of aromatic carbons (C(AR)) and aliphatic carbons (C(AL)) in each compound: log K(PE) = -0.241 + 0.313 C(AR) + 0.461 C(AL). The regression model is useful for the assessment of freely dissolved aqueous concentrations of alkylated-PAHs, which comprise a significant fraction of the total in petroleum-derived PAHs and in some pyrogenic PAH mixtures. For PCBs, experimentally determined octanol-water partitioning coefficients are the best predictor of the K(PE) values among the molecular parameters studied. The effect of salinity up to 20 or 30 parts per thousand is found to be relatively insignificant on K(PE) values for PAHs or PCBs, respectively.

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.

In Situ Sequestration of Hydrophobic Organic Contaminants in Sediments under Stagnant Contact with Activated Carbon. 1. Column Studies

The effectiveness of activated carbon (AC) treatment to sequester hydrophobic organic contaminants in sediments under stagnant contact was comprehensively studied for the first time. Two years of column experiments were conducted to simulate field conditions with two study sediments contaminated with petroleum and polychlorinated biphenyls, respectively, and variations in AC-sediment contact times, initial AC mixing regimes and distribution, AC particle sizes, and pore-water flow. The benefit of AC treatment was gradually enhanced with time toward the end point of the treatment, where sorption equilibrium is established between sediment and AC. After two years of stagnant contact, the contaminant uptake in polyethylene passive samplers embedded in the columns was reduced by 95-99% for polycyclic aromatic hydrocarbons and 93-97% for polychlorinated biphenyls with 5 and 4 wt % AC dose, respectively, when AC was initially applied by mechanical mixing. These results verify that AC treatment can effectively control the availability of hydrophobic organic contaminants under stagnant conditions within a reasonable time frame following an initial distribution of AC into the sediment. The effectiveness of AC treatment was strongly dependent on AC particle size and AC distribution, while the effect of AC initial mixing regimes and pore-water flow was not pronounced.

In Situ Sequestration of Hydrophobic Organic Contaminants in Sediments under Stagnant Contact with Activated Carbon. 2. Mass Transfer Modeling

The validity of a hydrophobic organic contaminant mass transfer model to predict the effectiveness of in situ activated carbon (AC) treatment under stagnant sediment-AC contact is studied for different contaminants and sediments. The modeling results and data from a previous 24-month column experiment of uptake in polyethylene samplers are within a factor of 2 for parent- and alkylated-polycyclic aromatic hydrocarbons in petroleum-impacted sediment and factors of 3-10 for polychlorinated biphenyls. The model successfully reproduces the relative effects of AC-sediment contact time, contaminant properties, AC particle size, AC mixing regime, AC distribution, and hydraulic conditions observed in the sediment column experiments. The model tracks contaminant concentrations in different sediment compartments over time, which provides useful information on the contaminant sequestration by the added AC. Long-term projection of the effectiveness of AC amendment using the model shows that the effects of AC particle size and particle-scale heterogeneity in AC distribution are pronounced within a year or so. However, the effect of those factors becomes less significant after a much longer contact period (on the order of a decade or two), resulting in substantial reduction in pore-water concentrations, for example, greater than 99% for benz[a]anthracene, under various scenarios.

Microbubble suspension as a carrier of oxygen and acclimated bacteria for phenanthrene biodegradation

The applicability of microbubble suspension made of saponin as a biodegradation-enhancing carrier where oxygen and pollutant-degraders are limited was studied. The saponin-microbubble suspension was used to deliver phenanthrene-degrading bacteria, inorganic nutrients, and oxygen. Bench-scale study was carried out to determine the physical properties of the microbubble suspension and to verify whether the delivered bacteria and oxygen were effectively used to degrade phenanthrene. A concentration of 2g saponin/L H(2)O generated stable microbubble suspension with a long half-drainage time and a high gas hold-up, and the addition of phenanthrene-degraders and inorganic salts to the saponin solution did not affect such properties. The flow of the microbubble suspension through a heterogeneous sand/clay-packed column occurred in two phases, with the liquid front advancing faster and the retarded gas front. The retarded gas front provided oxygen with bacteria, which enables phenanthrene biodegradation. Approximately 30% of the spiked phenanthrene was degraded in 21 days when one pore volume of 2.0 g/L saponin-microbubble suspension was applied whereas no phenanthrene decrease was observed following the application of the same saponin solution without microbubble generation. The decrease mainly occurred at the lower part of the column where the supply of oxygen by the microbubble was concentrated.

Enhancement of aerobic biodegradation in an oxygen-limiting environment using a saponin-based microbubble suspension

This study investigated the ability of a saponin-based microbubble suspension to enhance aerobic biodegradation of phenanthrene by subsurface delivery. As the microbubble suspension flowed through a sand column pressure buildup and release was repeatedly observed, which delivered oxygen to the less permeable regions. Burkholderia cepacia RPH1, a phenanthrene-degrading bacterium, was mainly transported in a suspended form in the microbubble suspension. When three pore volumes of the microbubble suspension containing B. cepacia RPH1 was introduced into a column contaminated with phenanthrene (100 mg/kg), the oxygen content declined to 5% from an initial value of 20% within 5 days and correspondingly, 34.4% of initial phenanthrene was removed in 8 days. The addition of two further three pore volumes enhanced the biodegradation efficiency by a factor of 2.2. Our data suggest that a saponin-based microbubble suspension could be a potential carrier for enhancing the aerobic biodegradation under an oxygen-limiting environment.

Secondary environmental impacts of remedial alternatives for sediment contaminated with hydrophobic organic contaminants.

This study evaluates secondary environmental impacts of various remedial alternatives for sediment contaminated with hydrophobic organic contaminants using life cycle assessment (LCA). Three alternatives including two conventional methods, dredge-and-fill and capping, and an innovative sediment treatment technique, in-situ activated carbon (AC) amendment, are compared for secondary environmental impacts by a case study for a site at Hunters Point Shipyard, San Francisco, CA. The LCA results show that capping generates substantially smaller impacts than dredge-and-fill and in-situ amendment using coal-based virgin AC. The secondary impacts from in-situ AC amendment can be reduced effectively by using recycled or wood-based virgin AC as production of these materials causes much smaller impacts than coal-based virgin AC. The secondary environmental impacts are highly sensitive to the dredged amount and the distance to a disposal site for dredging, the capping thickness and the distance to the cap materials for capping, and the AC dose for in-situ AC amendment. Based on the analysis, this study identifies strategies to minimize secondary impacts caused by different remediation activities: optimize the dredged amount, the capping thickness, or the AC dose by extensive site assessments, obtain source materials from local sites, and use recycled or bio-based AC.