Modeling of polychlorinated biphenyl removal from contaminated soil using steam

Microwave-generated steam technology shows promise as an effective remediation alternative for removal of polychlorinated biphenyls (PCBs) from contaminated soils, based on our laboratory-scale experiments. The overall process can be described by a nonisothermal, unsteady, coupled heat and multicomponent PCB mass-transport model in a multiphase, variably saturated, porous soil medium. In this paper, a multicomponent PCB mass-transport model is presented that assumes evaporation is an important removal mechanism and that is based on first-order mass transfer between the interface of PCB films and the bulk steam. The model was calibrated using the experimental data, and the calibrated model was verified by computational mass-balance checks and comparisons with laboratory-scale column experimental results. From a qualitative point of view, the calibrated model successfully simulated the transport of PCBs in variably saturated soil media. The calculated increase/decrease factors of physicochemical properties of PCBs as a function of temperature in the soil, water, and free phases were consistent with the model hypothesis of an evaporation process. The effects of mass-transfer coefficients and initial PCB concentrations in the soils on PCB removal rates were investigated using the numerical code. It was determined that the PCB removal rates were sensitive to mass-transfer coefficients and initial PCB concentrations. Although the steam:soil mass ratios required to achieve a given percentage removal were lower for lower initial PCB soil concentrations, steam: soil mass ratios required to achieve a given unit mass removal were higherfor lower initial PCB soil concentrations.     

Enantiomeric composition of chiral polychlorinated biphenyl atropisomers in aquatic bed sediment

Enantiomeric ratios (ERs) for eight polychlorinated biphenyl (PCB) atropisomers were measured in aquatic sediment from selected sites throughout the United States by using chiral gas chromatography/mass spectrometry. Nonracemic ERs for PCBs 91, 95, 132, 136, 149, 174, and 176 were found in sediment cores from Lake Hartwell, SC, which confirmed previous inconclusive reports of reductive dechlorination of PCBs at these sites on the basis of achiral measurements. Nonracemic ERs for many of the atropisomers were also found in bed-sediment samples from the Hudson and Housatonic Rivers, thus indicating that some of the PCB biotransformation processes identified at these sites are enantioselective. Patterns in ERs among congeners were consistent with known reductive dechlorination patterns at both river sediment basins. The enantioselectivity of PCB 91 is reversed between the Hudson and Housatonic River sites, which implies that the two sites have different PCB biotransformation processes with different enantiomer preferences.     

Enhanced reductive dechlorination of polychlorinated biphenyl impacted sediment by bioaugmentation with a dehalorespiring bacterium

Anaerobic reductive dehalogenation of commercial PCBs such as Aroclor 1260 has a critical role of transforming highly chlorinated congeners to less chlorinated congeners that are then susceptible to aerobic degradation. The efficacy of bioaugmentation with the dehalorespiring bacterium Dehalobium chlorocoercia DF1 was tested in 2-L laboratory mesocosms containing sediment contaminated with weathered Aroclor 1260 (1.3 ppm) from Baltimore Harbor, MD. Total penta- and higher chlorinated PCBs decreased by approximately 56% (by mass) in bioaugmented mesocosms after 120 days compared with no activity observed in unamended controls. Bioaugmentation with DF-1 enhanced the dechlorination of doubly flanked chlorines and stimulated the dechlorination of single flanked chlorines as a result of an apparent synergistic effect on the indigenous population. Addition of granulated activated carbon had a slight stimulatory effect indicating that anaerobic reductive dechlorination of PCBs at low concentrations was not inhibited by a high background of inorganic carbon that could affect bioavailability. The total number of dehalorespiring bacteria was reduced by approximately half after 60 days. However, a steady state level was maintained that was greater than the indigenous population of putative dehalorespiring bacteria in untreated sediments and DF1 was maintained within the indigenous population after 120 days. The results of this study demonstrate that bioaugmentation with dehalorespiring bacteria has a stimulatory effect on the dechlorination of weathered PCBs and supports the feasibility of using in situ bioaugmentation as an environmentally less invasive and lower cost alternate to dredging for treatment of PCB impacted sediments.     

Field-scale reduction of PCB bioavailability with activated carbon amendment to river sediments

Remediation of contaminated sediments remains a technological challenge because traditional approaches do not always achieve risk reduction goals for human health and ecosystem protection and can even be destructive for natural resources. Recent work has shown that uptake of persistent organic pollutants such as polychlorinated biphenyls (PCBs) in the food web is strongly influenced by the nature of contaminant binding, especially to black carbon surfaces in sediments. We demonstrate for the first time in a contaminated river that application of activated carbon to sediments in the field reduces biouptake of PCBs in benthic organisms. After treatment with activated carbon applied at a dose similar to the native organic carbon of sediment, bioaccumulation in freshwater oligochaete worms was reduced compared to preamendment conditions by 69 to 99%, and concentrations of PCBs in water at equilibrium with the sediment were reduced by greater than 93% at all treatment sites for up to three years of monitoring. By comparing measured reductions in bioaccumulation of tetra- and penta-chlorinated PCB congeners resulting from field application of activated carbon to a laboratory study where PCBs were preloaded onto activated carbon, it is evident that equilibrium sorption had not been achieved in the field. Although other remedies may be appropriate for some highly contaminated sites, we show through this pilot study that PCB exposure from moderately contaminated river sediments may be managed effectively through activated carbon amendment in sediments.     

Watershed processing of atmospheric polychlorinated biphenyl inputs

Indirect atmospheric deposition of PCBs was examined in subwatersheds of the Delaware River Estuary. Tributary PCB loads and atmospheric PCB concentrations were used to understand the pass-through efficiencies for nine rivers/ creeks for which PCB inputs appeared to be dominated by atmospheric deposition. The pass-through efficiency, E, was calculated from tributary loads and atmospheric deposition fluxes. Unfortunately, uncertainties in the gaseous and dry particle deposition velocities, vg and vd, respectively, render the calculated atmospheric deposition fluxes highly uncertain. In order to circumvent this problem, export of PCBs from the watershed was related directly to atmospheric PCB concentrations via a new mass transfer coefficient, the watershed delivery rate or vws, which describes the process by which the watershed transfers PCBs from the airto the River's main stem. vws increases with increasing chlorination and is significantly correlated with vapor pressure. This trend suggests that the transfer of PCBs from the atmosphere to the River via the watershed is more efficient for high molecular weight PCBs than for low molecular weight PCBs. This may indicate that the selected watersheds are at or close to equilibrium with respect to gaseous exchange of PCBs, such that lower molecular weight congeners undergo substantial revolatilization after deposition. The magnitude of the pass-through efficiency, E, depends on the deposition velocities used to calculate the atmospheric deposition flux, but when congener-specific deposition velocities are used, E is independent of vapor pressure and is relatively constant at about 3%.     

Elimination half-lives of polychlorinated biphenyl congeners in children

The elimination kinetics of polychlorinated biphenyls (PCBs) in humans is difficult to assess in observational studies, because PCB exposure is never completely abolished. In a community with high dietary PCB exposures from whale blubber, we examined two groups of children with increased body burdens from breast-feeding. Follow-up was from ages 4.5 to 7.5 years (99 subjects) and 7 to 14 years (101 subjects). The calculations were performed by the use of structural equation models, with adjustment for body weight and dietary blubber intake as the main source of postnatal exposure. As a likely result of background exposures, apparent elimination half-lives were unexpectedly long when based on results from all cohort members. Subjects with exposures above the median and in the highest quartile showed half-lives of about 3-4 years for CB-138 and 4.5-5.5 years for CB-105 and CB-118; 6.5-7.5 years for CB-156, CB-170, and CB-187; and 7-9 years for CB-153 and CB-180. The longest half-lives correspond to elimination of the parent PCB solely with a daily fat excretion rate of 1-2 g, whereas shorter half-lives assume metabolic break-down.     

Microcosm experiments to assess the effects of temperature and microbial activity on polychlorinated biphenyl transport in anaerobic sediment

Increased polychlorinated biphenyl (PCB) loadings from sediment to the water column under low-flow conditions during late spring and summer months have been observed in the Grasse River (Massena, NY) and other PCB-contaminated rivers in the United States. Temperature appears to be an important factor affecting this phenomenon, as increased sediment temperature leads to increased microbial and bioturbator activity as well as increased rates of diffusion and desorption. Laboratory-scale sediment microcosms were developed and used to study with fine-scale resolution the effects of temperature and microbial activity on PCB transport in river sediment. Over the time course of these experiments, with the extraction procedures used, irreversible sorption of each congener to sediment was observed and increased with aging of the sediment. Temperature-dependent transport was observed for PCB congeners 2,4,5-trichlorobiphenyl (BZ29), 2,5-dichlorobiphenyl (BZ9), and 2-chlorobiphenyl (BZ1) in Grasse River sediment and a synthetic sediment system. The fastesttransport of the congeners occurred in biologically active Grasse River sediment followed by biologically inactive (autoclaved) Grasse River sediment, and synthetic sediment. The increased transport in biologically active sediment demonstrated the importance of microbial activity, in particular gas bubble generation, in PCB transport in near-surface sediments.     

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.     

Apoptosis in bovine cumulus-oocyte complexes after exposure to polychlorinated biphenyl mixtures during in vitro maturation

Aroclor-1254 (A-1254) is a commercial mixture of coplanar (dioxin-like) and non-coplanar (non dioxin-like) polychlorinated biphenyls (PCBs) affecting bovine oocyte in vitro maturation (IVM) and developmental competence. In the present study, the role of cumulus cell apoptosis in mediating the toxic effects of PCBs during in vitro maturation has been investigated. Results indicate that exposure of cumulus-oocyte complexes (COCs) to A-1254 significantly induced apoptosis of cumulus cells. Furthermore, A-1254 significantly increased the expression of the pro-apoptotic gene, Bax, concomitantly reducing the level of the anti-apoptotic gene, Bcl-2, in the cumulus cell compartment. The effects of pure mixtures of coplanar (PCB 77, 126 and 169) or non-coplanar (PCB 52, 101 and 153) PCBs were examined. Exposure of COCs to coplanar PCBs affected maturation at doses as low as 100.6 pg/ml. Furthermore, a significant increase in apoptosis and in Bax mRNA expression was observed. No variations in maturation or apoptosis were observed in the non-coplanar PCB group. To further analyze the role of cumulus cells, COCs and denuded oocytes (DOs) have been exposed to A-1254 or coplanar PCBs during IVM. Exposure of COCs significantly reduced the percentage of matured oocytes after 24 h of culture in both treatments. In contrast, exposure of DOs significantly decreased the maturation rate only at the highest dose investigated (100-fold greater than that affecting COCs). Taken together, the results indicate a direct role of cumulus cell apoptosis in mediating PCB toxicity on bovine oocytes, and a direct relationship between congener planarity and toxicity in bovine oocytes is suggested.     

The determination of polychlorinated biphenyl residues: a review with special reference to foods

The determination of polychlorinated biphenyls presents several unique analytical problems, not least of which is the need to identify and quantify 209 possible analytes. Moreover, congener-specific analysis is essential because of structure-activity effects on toxicity and environmental stability. Although significant advances have been achieved in identification/quantification procedures with the aid of highly efficient, inert open tubular chromatography columns and coupled GC-MS, sampling and extraction procedures have not developed to the same extent. The primary focus of this review is the determination of polychlorinated biphenyls in foods. However, the problems of separation and identification overshadow the importance of the sample matrix, and relevant data from other areas of analysis are quoted.     

Modeling effective diffusivity of volatile organic compounds in activated carbon fiber

Volatile organic compounds (VOCs) comprise 67% of total hazardous air pollutants (HAPs) that are emitted by major industrial point sources into the U.S. atmosphere (1). Adsorption by activated carbon fiber (ACF) has been recognized as one of the feasible regenerative control processes to separate and recover VOCs for reuse. Characteristics of VOCs transport in ACFs are required to efficiently design ACF sorption systems. However, extensive resources are spent experimentally obtaining transient sorption data to design adsorption systems. As an alternative, this work develops a new model that predicts effective diffusivities of VOCs into ACFs. The diffusion process is modeled as Knudsen transport into the ACF open pore spaces coupled with activated surface diffusion on the ACF's internal surface area. Temperature and Darken's factors are included in the surface diffusion model to provide corrections for thermodynamic state and deviation from Fick's Law, respectively. Depth of the adsorption potential well is considered as the product of the heat of adsorption of a reference VOC, an adsorption similarity factor, and a surface diffusion energy factor. Introduction of the adsorption similarity factor in the effective diffusivity model is a new concept providing a means to predict effective diffusivity of similar adsorption systems from a reference system. Experimental data from a short length column are used to determine effective diffusivity of acetone in ACF. Results from this diffusivity model are compared to experimental values for the acetone/ACF system to describe the degree of closure between modeled and experimental results.     

Effects of organic carbon supply rates on uranium mobility in a previously bioreduced contaminated sediment

Bioreduction-based strategies for remediating uranium (U)-contaminated sediments face the challenge of maintaining the reduced status of U for long times. Because groundwater influxes continuously bring in oxidizing terminal electron acceptors (O2, NO3(-)), it is necessary to continue supplying organic carbon (OC) to maintain the reducing environment after U bioreduction is achieved. We tested the influence of OC supply rates on mobility of previously microbial reduced uranium U(IV) in contaminated sediments. We found that high degrees of U mobilization occurred when OC supply rates were high, and when the sediment still contained abundant Fe(III). Although 900 days with low levels of OC supply minimized U mobilization, the sediment redox potential increased with time as did extractable U(VI) fractions. Molecular analyses of total microbial activity demonstrated a positive correlation with OC supply and analyses of Geobacteraceae activity (RT-qPCR of 16S rRNA) indicated continued activity even when the effluent Fe(II) became undetectable. These data support our hypothesis on the mechanisms responsible for remobilization of U under reducing conditions; that microbial respiration caused increased (bi)carbonate concentration and formation of stable uranyl carbonate complexes, thereby shifted U(IV)/U(VI) equilibrium to more reducing potentials. The data also suggested that low OC concentrations could not sustain the reducing condition of the sediment for much longer time. Bioreduced U(IV) is not sustainable in an oxidizing environment for a very long time.     

Effect of activated carbon amendment on bacterial community structure and functions in a PAH impacted urban soil

We collected urban soil samples impacted by polycyclic aromatic hydrocarbons (PAHs) from a sorbent-based remediation field trial to address concerns about unwanted side-effects of 2% powdered (PAC) or granular (GAC) activated carbon amendment on soil microbiology and pollutant biodegradation. After three years, total microbial cell counts and respiration rates were highest in the GAC amended soil. The predominant bacterial community structure derived from denaturing gradient gel electrophoresis (DGGE) shifted more strongly with time than in response to AC amendment. DGGE band sequencing revealed the presence of taxa with closest affiliations either to known PAH degraders, e.g. Rhodococcus jostii RHA-1, or taxa known to harbor PAH degraders, e.g. Rhodococcus erythropolis, in all soils. Quantification by real-time polymerase chain reaction yielded similar dioxygenases gene copy numbers in unamended, PAC-, or GAC-amended soil. PAH availability assessments in batch tests showed the greatest difference of 75% with and without biocide addition for unamended soil, while the lowest PAH availability overall was measured in PAC-amended, live soil. We conclude that AC had no detrimental effects on soil microbiology, AC-amended soils retained the potential to biodegrade PAHs, but the removal of available pollutants by biodegradation was most notable in unamended soil.     

Effects of inhibitors on anaerobic microbial consortium with enhanced dechlorination activity in polychlorinated biphenyl mixture

Characterization was carried out on the anaerobic microbial consortium with enhanced degradation activity toward polychlorinated biphenyls in Kanechlor-300 and Kanechlor-400 mixtures in a burnt soil (BS) culture. The addition of molybdate to the BS culture resulted in the accumulation of less-chlorinated biphenyls such as 4,4'-dichlorinated biphenyl and 2,3',4-trichlorinated biphenyl; however, no such accumulation occurred without molybdate supplementation. No significant effect was observed in individual congeners in the BS culture supplemented with 2-bromoethane sulfonic acid. Analyses involving both the polymerase chain reaction-denaturing gradient gel electrophoresis of partial 16S rRNA genes and respiratory quinones showed that the predominant microorganisms in the BS culture were anaerobic Firmicutes, while sulfate reducers of the phyla Deltaproteobacteria, Firmicutes and Chloroflexi were absent in the culture amended with the inhibitors. No positive correlation was observed between the dechlorination activity and a PCR-based detection of gene fragments of known dechlorinating bacteria. These results suggest that sulfate reducers played an important role in the enhanced anaerobic dechlorination of PCBs in the BS culture.     

Biodynamic modeling of PCB uptake by Macoma balthica and Corbicula fluminea from sediment amended with activated carbon

Activated carbon amendment was assessed in the laboratory as a remediation strategy for freshwater sediment contaminated with polychlorinated biphenyls (PCBs) from the Grasse River (near Massena, NY). Three end points were evaluated: aqueous equilibrium PCB concentration, uptake into semipermeable membrane devices (SPMDs), and 28-day bioaccumulation in the clam Corbicula fluminea. PCB uptake by water, SPMDs, and clams followed similar trends, with reductions increasing as a function of carbon dose. Average percent reductions in clam tissue PCBs were 67, 86, and 95% for activated carbon doses of 0.7, 1.3, and 2.5% dry wt, respectively. A biodynamic model that incorporates sediment geochemistry and dietary and aqueous uptake routes was found to agree well with observed uptake by C. fluminea in our laboratory test systems. Results from this study were compared to 28-day bioaccumulation experiments involving PCB-contaminated sediment from Hunters Point Naval Shipyard (San Francisco Bay, CA) and the clam Macoma balthica. Due to differences in feeding strategy, M. balthica deposit-feeds whereas C. fluminea filter-feeds, the relative importance of the aqueous uptake route is predicted to be much higher for C. fluminea than for M. balthica. Whereas M. balthica takes up approximately 90% of its body burden through sediment ingestion, C. fluminea only accumulates approximately 45% via this route. In both cases, results strongly suggest that it is the mass transfer of PCBs from native sediment to added carbon particles, not merely reductions in aqueous PCB concentrations, that effectively reduces PCB bioavailability and uptake by sediment-dwelling organisms.