PubMed Health⌕ Search

Biomedical subjects

Richard G Luthy

Publications and source records attributed to Richard G Luthy.

At least 19 recordsLinked to original sources
PubMed2006

Sorption of perfluorinated surfactants on sediments.

The sorption of anionic perfluorochemical (PFC) surfactants of varying chain lengths to sediments was investigated using natural sediments of varying iron oxide and organic carbon content. Three classes of PFC surfactants were evaluated for sorptive potential: perfluorocarboxylates, perfluorosulfonates, and perfluorooctyl sulfonamide acetic acids. PFC surfactant sorption was influenced by both sediment-specific and solution-specific parameters. Sediment organic carbon, rather than sediment iron oxide content, was the dominant sediment-parameter affecting sorption, indicating the importance of hydrophobic interactions. However, sorption also increased with increasing solution [Ca2+] and decreasing pH, suggesting that electrostatic interactions play a role. Perfluorocarbon chain length was the dominant structural feature influencing sorption, with each CF2 moiety contributing 0.50-0.60 log units to the measured distribution coefficients. The sulfonate moiety contributed an additional 0.23 log units to the measured distribution coefficient, when compared to carboxylate analogs. In addition, the perfluorooctyl sulfonamide acetic acids demonstrated substantially stronger sorption than perfluorooctane sulfonate (PFOS). These data should prove useful for modeling the environmental fate of this class of contaminants.

Adsorption↗
PubMed2006

Fluorochemical mass flows in a municipal wastewater treatment facility.

Fluorochemicals have widespread applications and are released into municipal wastewater treatment plants via domestic wastewater. A field study was conducted at a full-scale municipal wastewater treatment plant to determine the mass flows of selected fluorochemicals. Flow-proportional, 24 h samples of raw influent, primary effluent, trickling filter effluent, secondary effluent, and final effluent and grab samples of primary, thickened, activated, and anaerobically digested sludge were collected over 10 days and analyzed by liquid chromatography electrospray-ionization tandem mass spectrometry. Significant decreases in the mass flows of perfluorohexane sulfonate and perfluorodecanoate occurred during trickling filtration and primary clarification, while activated sludge treatment decreased the mass flow of perfluorohexanoate. Mass flows of the 6:2 fluorotelomer sulfonate and perfluorooctanoate were unchanged as a result of wastewater treatment, which indicates that conventional wastewater treatment is not effective for removal of these compounds. A net increase in the mass flows for perfluorooctane and perfluorodecane sulfonates occurred from trickling filtration and activated sludge treatment. Mass flows for perfluoroalkylsulfonamides and perfluorononanoate also increased during activated sludge treatment and are attributed to degradation of precursor molecules.

Chromatography, Liquid↗
PubMed2006

Nanometer-scale chemical heterogeneities of black carbon materials and their impacts on PCB sorption properties: soft X-ray spectromicroscopy study.

Synchrotron-based soft X-ray spectromicroscopy was used to probe nanometer-scale chemical heterogeneities of black carbon (BC) materials, including anthracite coal, coke, and activated carbon (AC), and to study their impact on the partitioning of one type of polychlorinated biphenyls (PCB-166: 2,3,4,4',5,6 hexachloro biphenyl) onto AC particles. Various carbon species (e.g., aromatic, ketonic/ phenolic, and carboxylic functional groups) were found in all of the BC materials examined, and impurities (e.g., carbonate and potassium ions in anthracite coal) were identified in nanometer-scale regions of these samples. We show that these chemical heterogeneities in AC particles influence their sorption of hydrophobic organic compounds (HOCs). PCB-166 was found to accumulate preferentially on AC particles with the highest content of aromatic functionalities. These new findings from X-ray spectromicroscopy have the following implications for the role of BC materials in the environment: (1) the functional groups of BC materials vary on a 25-nanometer scale, and so does the abundance of the HOCs; (2) molecular-level characterization of HOC sorption preferences on AC will lead to an improved understanding of AC sorption properties for the remediation of HOCs in soils and sediments.

Adsorption↗
PubMed2006

New perspectives on perfluorochemical ecotoxicology: inhibition and induction of an efflux transporter in the marine mussel, Mytilus californianus.

The toxicological effects of perfluoroalkyl acids on the p-glycoprotein (p-gp) cellular efflux transporter were investigated using the marine mussel Mytilus californianus as a model system. Four of the perfluoroalkyl acids studied exhibit chemosensitizing behavior, significantly inhibiting p-gp transporter activity. The inhibitory potency is maximal for the longer chain acids perfluorononanoate (PFNA) and perfluorodecanoate (PFDA), with average IC50 values of 4.8 and 7.1 microM, respectively. Results indicate that PFNA inhibits p-gp by an indirect mechanism, and this inhibition is reversible and accompanied by a rapid loss of PFNA from the tissue. In addition, PFNA induces expression of the p-gp transporter after a 2-h exposure, a stress response that may result in a metabolic cost to the organism. Given that most organisms, including humans, share efflux transporters as a first line of defense against toxicants, the results of this study may have broader implications for the ecotoxicology of perfluoroalkyl acids.

ATP Binding Cassette Transporter, Subfamily B↗
PubMed2006

Modeling polychlorinated biphenyl mass transfer after amendment of contaminated sediment with activated carbon.

The sorption kinetics and concentration of polychlorinated biphenyls (PCBs) in historically polluted sediment is modeled to assess a remediation strategy based on in situ PCB sequestration by mixing with activated carbon (AC). We extend our evaluation of a model based on intraparticle diffusion by including a biomimetic semipermeable membrane device (SPMD) and a first-order degradation rate for the aqueous phase. The model predictions are compared with the previously reported experimental PCB concentrations in the bulk water phase and in SPMDs. The simulated scenarios comprise a marine and a freshwater sediment, four PCB congeners, two AC grain sizes, four doses of AC, and comparison with laboratory experiments for up to 540 days of AC amendment slowly mixed with sediment. The model qualitatively reproduces the observed shifts in the PCB distribution during repartitioning after AC amendment but systematically overestimates the overall effect of the treatment in reducing aqueous and SPMD concentrations of PCBs by a factor of 2-6. For our AC application in sediment, competitive sorption of the various solutes apparently requires a reduction by a factor of 16 of the literature values for the AC-water partitioning coefficient measured in pure aqueous systems. With this correction, model results and measurements agree within a factor of 3. We also discuss the impact of the nonlinearity of the AC sorption isotherm and first-order degradation in the aqueous phase. Regular mixing of the sediment accelerates the benefit of the proposed amendment substantially. But according to our scenario, after AC amendment is homogeneously mixed into the sediment and then left undisturbed, aqueous PCB concentrations tend toward the same reduction after approximately 5 or more years.

Absorption↗
PubMed2005

Phenanthrene and pyrene sorption and intraparticle diffusion in polyoxymethylene, coke, and activated carbon.

We report sorption isotherms and uptake kinetics for phenanthrene and pyrene with three organic model sorbents: polyoxymethylene (POM), coke, and activated carbon. We combine batch equilibration and kinetic experiments with the direct observation of the long-term diffusion of phenanthrene and pyrene as measured within cross-sectioned particles using microprobe laser-desorption laser-ionization mass spectroscopy (muL2MS). For POM pellets, the intraparticle concentration profiles predicted from kinetic batch experiments and a polymer diffusion model with spherical geometry are in agreement with the independent muL2MS measurements. For coke particles, the apparent diffusivities decreased with smaller particle size. These trends in diffusivities were described by a sorption-retarded pore diffusion model with a particle-size-dependent solid-water partitioning coefficient obtained from apparent equilibrium observed in the kinetic batch studies. For activated carbon, the muL2MS measurements showed faster radial diffusion of phenanthrene and pyrene into the particle interior than predicted from diffusion models based on a single sorption domain and diffusivity. A branched pore kinetic model, comprising polycyclic aromatic hydrocarbon (PAH) macropore diffusion with kinetic exchange of PAH between macroporous and microporous domains, fits the experimental observations better. Because of parallel macro- and microdiffusion processes, nonlinear sorption isotherms, and a concentration-dependent diffusivity, it is not possible to make independent parameter estimations for intraparticle diffusion in activated carbon using our present procedures.

Adsorption↗
PubMed2005

Quantitative determination of perfluorochemicals in sediments and domestic sludge.

Perfluorochemicals (PFCs) are the subject of increasingly intense environmental research. Despite their detection both in biota and in aqueous systems, little attention has been paid to the possible presence of this class of compounds in solid environmental matrixes. The limited available data indicate that some PFCs such as perfluorooctane sulfonate (PFOS) may strongly sorb to solids, and sewage sludge is widely suspected as a major sink of PFCs entering municipal waste streams. A quantitative analytical method was developed that consists of liquid solvent extraction of the analytes from sediments and sludge, cleanup via solid-phase extraction, and injection of the extracts with internal standards into a high-performance liquid chromatography (HPLC) system coupled to a tandem mass spectrometer (LC/MS/MS). The limits of detections of the method were analyte and matrix dependent, but ranged from 0.7 to 2.2 ng/g and 0.041 to 0.246 ng/g (dry weight) for sludge and sediment, respectively. A demonstration of the method was performed by conducting a limited survey of domestic sludge and sediments. The concentration of PFCs in domestic sludge ranged from 5 to 152 ng/g for total perfluorocarboxylates and 55 to 3370 ng/g for total perfluoroalkyl sulfonyl-based chemicals. Data from a survey of San Francisco Bay Area sediments suggest widespread occurrence of PFCs in sediments at the low ng/g to sub-ng/g level. Furthermore, substances that may be transformed to PFOS, such as 2-(N-ethylperfluorooctanesulfonamido) acetic acid (N-EtFOSAA) and 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA), are present in both sediments and sludge at levels often exceeding PFOS.

Alkanesulfonic Acids↗
PubMed2005

Addition of activated carbon to sediments to reduce PCB bioaccumulation by a polychaete (Neanthes arenaceodentata) and an amphipod (Leptocheirus plumulosus).

This work examines the effects of adding coke or activated carbon on the bioavailability of polychlorinated biphenyls (PCBs) in contaminated sedimentfrom South Basin at Hunters Point, San Francisco Bay. We show with 28-day sediment exposure tests that PCB bioaccumulation in a polychaete (Neanthes arenaceodentata) is reduced by 82% following 1-month contact of sediment with activated carbon and by 87% following 6-months contact of sediment with activated carbon. PCB bioaccumulation in an amphipod (Leptocheirus plumulosus) is reduced by 70% following 1-month contact of sediment with activated carbon and by 75% after 6-months contact of sediment with activated carbon. Adding coke had a negligible effect on reducing PCB bioaccumulation, probably because of the low specific surface area and the slow kinetics of PCB diffusion intothe solid coke particles. Reductions in congener bioaccumulation with activated carbon were inversely related to congener Kow, suggesting that the efficacy of activated carbon is controlled by the mass-transfer rate of PCBs from sediment and into activated carbon. We find that reductions in aqueous PCB concentrations in equilibrium with the sediment were similar to reductions in PCB bioaccumulation. While no lethality was observed following activated carbon addition, growth rates were reduced by activated carbon for the polychaete, but not for the amphipod, suggesting the need for further study of the potential impacts of activated carbon on exposed communities. The study suggests that treatment of the biologically active layer of contaminated sediments with activated carbon may be a promising in-situ technique for reducing the bioavailability of sediment-associated PCBs and other hydrophobic organic compounds.

Amphipoda↗
PubMed2005

The sequestration of PCBs in Lake Hartwell sediment with activated carbon.

Recent laboratory studies with a marine sediment from a tidal mudflat in San Francisco Bay demonstrated that a low dose of activated carbon enhances the sequestration of PCBs and PAHs under well-mixed conditions. Here we compare activated carbon treatment for a freshwater sediment from a rural site, using PCB-contaminated sediment from Lake Hartwell, SC. An activated carbon dose of 2% of the dry sediment mass lowered total aqueous PCB concentrations by more than 95% after 1 month of treatment and more than 98% after 6 months. Aqueous PCB concentrations remained below detection limits following 18 months of sediment-carbon contact in slowly mixed systems. Uptake of PCBs into semipermeable membrane devices was reduced by 78%, 91% and 97% over 1, 6 and 18 months, respectively. These tests show that PCB sequestration with activated carbon improves with contact time and is not diminished by prolonged mixing with sediment. Desorption studies confirmed the sequestration, in which 74% of the total PCB mass could be desorbed from untreated Lake Hartwell sediment within 30 days as compared to only 7% after activated carbon treatment for 6 months. We compare these observations with marine sediment from San Francisco Bay and propose a conceptual model to rationalize how sediment properties relate to the reduction in aqueous PCB concentrations during activated carbon treatment.

Carbon↗
PubMed2005

Effects of dose and particle size on activated carbon treatment to sequester polychlorinated biphenyls and polycyclic aromatic hydrocarbons in marine sediments.

Recent laboratory studies show that mixing activated carbon with contaminated sediment reduces the chemical and biological availability of hydrophobic organic contaminants. In this study, we test the effects of varying the activated carbon dose and particle size in reducing the aqueous availability of polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) and the uptake of PCBs by two benthic organisms. We mixed PCB- and PAH-contaminated sediment from Hunters Point Naval Shipyard, San Francisco Bay (CA, USA), for one month with activated carbon, at doses of 0.34, 1.7, and 3.4% dry mass basis. We found that increasing the carbon dose increased the effectiveness in reducing PCB bioaccumulation. In 56-d uptake tests with the benthic organisms Neanthes arenaceodentata and Leptocheirus plumulosus, PCB bioaccumulation was reduced by 93 and 90%, respectively, with 3.4% carbon. Increasing the dose also increased the effectiveness in reducing PCB and PAH aqueous concentrations and uptake by semipermeable membrane devices and quiescent flux of PCBs to overlying water. Decreasing activated carbon particle size increased treatment effectiveness in reducing PCB aqueous concentration, and larger-sized activated carbon (400-1,700 microm) was ineffective with a contact period of one month. We invoke a numerical model based on intraparticle diffusion in sediment and activated carbon particles to help interpret our experimental results. This model was useful in explaining the trends for the effect of activated carbon dose and particle size on PCB aqueous concentrations in well-mixed systems.

Carbon↗
PubMed2005

Physicochemical characterization of coke-plant soil for the assessment of polycyclic aromatic hydrocarbon availability and the feasibility of phytoremediation.

Coke oven site soil was characterized to assess the particle association and availability of polycyclic aromatic hydrocarbons (PAHs). We identified various carbonaceous materials including coal, coke, pitch, and tar decanter sludge. Most of the PAHs were associated with the polymeric matrix of tar sludge or hard pitch as discrete particles, coatings on soil mineral particles, or complex aggregates. The PAH availability from these particles was very low due to hindered diffusive release from solid tar or pitch with apparent diffusivities of 6 x 10(-15) for phenanthrene, 3 x 10(-15) for pyrene, and 1 x 10(-15) cm2/s for benzo[a]pyrene. Significant concentrations of PAHs were observed in the interior of solid tar aggregates with up to 40,000 mg/kg total PAHs. The release of PAHs from the interior of such particles requires diffusion over a substantial distance, and semipermeable membrane device tests confirmed a very limited availability of PAHs. These findings explain the results from three years of phytoremediation of the site soil, for which no significant changes in the total PAH concentrations were observed in the test plot samples. The observed low bioavailability of PAHs probably inhibited PAH phytoremediation, as diffusion-limited mass transfer would limit the release of PAHs to the aqueous phase.

Acetone↗
PubMed2005

Improving risk assessments for manufactured gas plant soils by measuring PAH availability.

Remediation of soils at oil-gas manufactured gas plant (MGP) sites is driven primarily by the human health risks posed by the carcinogenic polycyclic aromatic hydrocarbons (PAHs), particularly benzo[a]pyrene (BaP), that are associated with lampblack residues. Although PAHs on lampblack are tightly sorbed, risk assessments do not account for this reduced availability. A multi-investigator study of 7 oil-gas MGP site soil samples demonstrated that the dermal and ingestion absorption factors are far lower than current default assumptions used in risk assessments. Using these sample-specific absorption factors in standard risk assessment equations increased risk-based cleanup levels by a factor of 72 on average (with a range from 23 to 142 times the default level). The rapidly released fraction of the BaP in each sample, as measured by supercritical fluid extraction, was closely correlated (r2 = 0.96) to these calculated cleanup levels. The weight of evidence developed during this research indicates that the risks posed by PAHs on lampblack are far less than assumed when using default absorption factors and that a tiered evaluation protocol employing chemical analyses, chemical release data, and in vitro bioassays can be used to establish more realistic site-specific criteria.

Absorption↗
PubMed2004

Addition of carbon sorbents to reduce PCB and PAH bioavailability in marine sediments: physicochemical tests.

The addition of activated carbon as particulate sorbent to the biologically active layer of contaminated sediment is proposed as an in-situ treatment method to reduce the chemical and biological availability of hydrophobic organic contaminants (HOCs) such as polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs). We report results from physicochemical experiments that assess this concept. PCB- and PAH-contaminated sediment from Hunters Point Naval Shipyard, San Francisco Bay, CA, was contacted with coke and activated carbon for periods of 1 and 6 months. Sediment treated with 3.4 wt % activated carbon showed 92% and 84% reductions in aqueous equilibrium PCB and PAH concentrations, 77% and 83% reductions in PCB and PAH uptake by semipermeable membrane devices (SPMD), respectively, and reductions in PCB flux to overlying water in quiescent systems up to 89%. Adding coke to contaminated sediment did not significantly decrease aqueous equilibrium PCB concentrations nor PCB or PAH availability in SPMD measurements. Coke decreased PAH aqueous equilibrium concentrations by 38-64% depending on coke dose and particle size. The greater effectiveness of activated carbon as compared to coke is attributed to its much greater specific surface area and a pore structure favorable for binding contaminants. The results from the physicochemical tests suggest that adding activated carbon to contaminated field sediment reduces HOC availability to the aqueous phase. The benefit is manifested relatively quickly under optimum contact conditions and improves in effectiveness with contact time from 1 to 6 months. Activated carbon application is a potentially attractive method for in-situ, nonremoval treatment of marine sediment contaminated with HOCs.

Adsorption↗
PubMed2004

Effects of particulate carbonaceous matter on the bioavailability of benzo[a]pyrene and 2,2',5,5'-tetrachlorobiphenyl to the clam, Macoma balthica.

We investigated the bioavailability via diet of spiked benzo[a]pyrene (BaP) and 2,2',5,5'-tetrachlorobiphenyl (PCB-52) from different carbonaceous (non-carbonate, carbon containing) particle types to clams (Macoma balthica) collected from San Francisco Bay. Our results reveal significant differences in absorption efficiency between compounds and among carbonaceous particle types. Absorption efficiency for PCB-52 was always greater than that for BaP bound to a given particle type. Among particles, absorption efficiency was highest from wood and diatoms and lowest from activated carbon. Large differences in absorption efficiency could not be simply explained by comparatively small differences in the particles' total organic carbon content. BaP and PCB-52 bound to activated carbon exhibited less than 2% absorption efficiency and were up to 60 times less available to clams than the same contaminants associated with other types of carbonaceous matter. These results suggest that variations in the amount and type of sediment particulate carbonaceous matter, whether naturally occurring or added as an amendment, will have a strong influence on the bioavailability of hydrophobic organic contaminants. This has important implications for environmental risk assessment, sediment management, and development of novel remediation techniques.

Absorption↗
PubMed2003

PAH sorption mechanism and partitioning behavior in lampblack-impacted soils from former oil-gas plant sites.

This study assessed polycyclic aromatic hydrocarbon (PAH) association and aqueous partitioning in lampblack-impacted field soils from five sites in California that formerly housed oil-gas process operations. Lampblack is the solid residue resulting from the decomposition of crude oil at high temperatures in the gas-making operation and is coated or impregnated with oil gasification byproducts, among which PAHs are the compounds of the greatest regulatory concern. A suite of complementary measurements investigated the character of lampblack particles and PAH location and the associated effects on PAH partitioning between lampblack and water. PAH analyses on both whole samples and density-separated components demonstrated that 81-100% of PAHs in the lampblack-impacted soils was associated with lampblack particles. FTIR, 13C NMR, and SEM analyses showed that oil-gas lampblack solids comprise primarily aromatic carbon with soot-like structures. A free-phase aromatic oil may be present in some of the lampblack soils containing high PAH concentrations. Comparable long-term aqueous partitioning measurements were obtained with an air-bridge technique and with a centrifugation/alum flocculation procedure. Large solid/water partition coefficient (Kd) values were observed in samples exhibiting lower PAH and oil levels, whereas smaller Kd values were measured in lampblack samples containing high PAH levels. The former result is in agreement with an oil-soot partitioning model, and the latter is in agreement with a coal tar-water partitioning model. Lampblack containing high PAH levels appears to exhaust the sorption capacity of the soot-carbon, creating a free aromatic oil phase that exhibits partitioning behavior similar to PAHs in coal tar. This study improves mechanistic understanding of PAH sorption on aged lampblack residuals at former oil-gas sites and provides a framework for mechanistic assessment of PAH leaching potential and risk from such site materials.

Carbon↗
PubMed2003

PCB and PAH speciation among particle types in contaminated harbor sediments and effects on PAH bioavailability.

This research provides particle-scale understanding of PCB and PAH distribution in sediments obtained from three urban locations in the United States: Hunters Point, CA; Milwaukee Harbor, WI; and Harbor Point, NY. The sediments comprised mineral grains (primarily sand, silt, and clays) and carbonaceous particles (primarily coal, coke, charcoal, pitch, cenospheres, and wood). The carbonaceous sediment fractions were separated from the mineral fractions based on their lower density and were identified by petrographic analysis. In all three sediments, carbonaceous particles contributed 5-7% of the total mass and 60-90% of the PCBs and PAHs. The production of carbonaceous particles is not known to be associated with PCB contamination, and it is very unlikely that these particles can be the source of PCBs in the environment Thus, it appears that carbonaceous particles preferentially accumulate PCBs acting as sorbents in the aqueous environment if PCBs are released directly to the sediment or if deposited as airborne soot particles. Aerobic bioslurry treatment resulted in negligible PAH loss from the carbonaceous coal-derived material in Milwaukee Harbor sediment but resulted in 80% of the PAHs being removed from carbonaceous particles in Harbor Point sediment. Microscale PAH extraction and analysis revealed that PAHs in Harbor Point sediment were associated mainly with coal tar pitch residue. PAHs present in semisolid coal tar pitch are more bioavailable than PAHs sorbed on carbonaceous particles such as coal, coke, charcoal, and cenosphere. Results of this study illustrate the importance of understanding particle-scale association of hydrophobic organic contaminants for explaining bioavailability differences among sediments.

Adsorption↗
PubMed2003

Evaluation and testing of analytical methods for cyanide species in municipal and industrial contaminated waters.

Total cyanide analysis by distillation is used most commonly to assess cyanide content of water samples. This manual method is robust but slow and provides no information about cyanide speciation, a significant limitation in that cyanide species have substantially different toxicity characteristics. Seven alternative methods for the analysis of cyanide species or groups of species were evaluated in reagent water and five different contaminated water matrices, including five species-specific methods--weak acid dissociable (WAD) cyanide, free cyanide by microdiffusion, available cyanide, automated WAD cyanide by thin film distillation, metal cyanides by ion chromatography--and two automated techniques for total cyanide--total cyanide bythin film distillation and total cyanide by low-power UV digestion. The species-specific cyanide analytical techniques achieved low, ppb-level detection limits and exhibited satisfactory accuracy and precision for most contaminated waters. Analysis of low concentrations of cyanide species in raw wastewater was problematical for the available cyanide and ion chromatography methods, which experienced significant interference problems and/or low recoveries. There was recovery of significant diffusible cyanide in microdiffusion tests with nickel-cyanide-spiked samples, reflecting dissociation of this weak metal-cyanide complex during the test and demonstrating that the test can recover some fraction of WAD cyanide in addition to free cyanide. The automated total cyanide methods, which involve UV digestion, achieved low detection limits for most waters but exhibited low recoveries for some waters.

Chromatography, Ion Exchange↗