Biomedical subjects

William D Marshall

Publications and source records attributed to William D Marshall.

8 recordsLinked to original sources

PubMed2006

A washing procedure to mobilize mixed contaminants from soil: I. Polychlorinated biphenyl compounds.

We conducted a laboratory study to assess the feasibility of a washing process with nonionic and anionic surfactants in combination with ethylenediaminetetraacetate (EDTA) for the simultaneous mobilization of heavy metals and polychlorinated biphenyls (PCBs) from a field-contaminated soil. Unit processes consisting of complexometric extraction and surfactant-assisted mobilization were combined with reagent regeneration and detoxification steps to generate innocuous products. Ten minutes of ultrasonic mixing of the soil with a combination of 30 mL L(-1) surfactant suspension and a sparing quantity (2 mmol) of EDTA mobilized appreciable quantities of PCBs, virtually all of the available Cd, Cu, Mn, and Pb, and lesser amounts of the Zn, Ni, and Cr but only small quantities of Al and Fe. Relative to individual reagents, combinations of surfactant (Brij 98, Triton X-301, or Triton XQS-20) with EDTA did not influence PCB extraction efficiencies perceptibly. Of the three surfactants, the Brij 98 proved to be the most efficient for three successive extractions with a single charge, mobilizing 83% of the PCBs, whereas companion extractions that used fresh reagent each time mobilized 87% of the soil PCB content. The decreased PCB mobilization with the same quantity of anionic surfactant (71 or 68%) resulted from losses during the EDTA regeneration process with zero-valent Mg. In toto, these studies demonstrate that PCB compounds and selected heavy metals can be coextracted efficiently from soil with three successive washes with the same washing suspension containing EDTA and a nonionic surfactant.

Chelating Agents↗

PubMed2006

A washing procedure to mobilize mixed contaminants from soil: II. Heavy metals.

We conducted a laboratory study to assess the efficiency of nonionic and anionic surfactants in combination with a sparing quantity of ethylenediaminetetraacetate (EDTA) to simultaneously extract heavy metals (HMs) and polychlorinated biphenyl (PCB) compounds from a field-contaminated soil. A soil wash that mobilized both HMs and PCBs was combined with back-extraction with hexane to remove PCBs from the aqueous wash. The aqueous washing suspension was then regenerated by precipitation of the HMs induced by corrosion and hydrolysis of zero-valent Mg to provide a cleaned soil and innocuous extract. Finally, the washing suspension was recycled twice to mobilize more contaminants from the soil particulate fraction. After ultrasonic equilibration, EDTA in admixture with a nonionic surfactant did not appreciably change the efficiency of mobilization of most heavy metals (Al, Cd, Cr, Fe Mn, Ni, and Zn), but did increase the recovery of Cu and Pb. The release of EDTA from HM complexes was efficient for most metals (99%) but was influenced by the chemical characteristics of the surfactant. The EDTA recovery (62-65%) after three cycles of soil washing, hexane back-extraction, and Mg(0) treatment was similar for all reagent combinations. In toto, these studies demonstrate that after treatment with ultrasound, selected heavy metals can be coextracted efficiently from soil with a single washing suspension containing EDTA and a nonionic surfactant.

Adsorption↗

PubMed2005

Catalytic hydrogenation of polycyclic aromatic hydrocarbons over palladium/gamma-Al2O3 under mild conditions.

As a prelude to the optimization of a continuous decontamination system, catalytic hydrogenations of selected tri-, tetra- and penta-cyclic aromatic hydrocarbon compounds over commercial alumina supported palladium were investigated under mild conditions ( approximately 90 degrees C/0.42 MPa H2) and interpreted in the light of reports from the literature. Acenaphthylene, acenaphthene, anthracene, phenanthrene, chrysene and benzo[alpha]pyrene were hydrogenated, virtually completely, to saturated polycyclic hydrocarbon compounds with no appreciable evidence of carbon-carbon bond rearrangement during equilibration. With comparable operating conditions, triphenylene was only partially hydrogenated; the central ring remained unsaturated. The effects of reaction temperature, time of equilibration and supporting gases on hydrogenation were evaluated. Whereas near-critical CO2 had no perceptible influence on rate/course of the reaction, nitrogen decreased the reaction rate somewhat.

Aluminum Oxide↗

PubMed2005

Effect of surfactant alkyl chain length on soil cadmium desorption using surfactant/ligand systems.

The effect of surfactant alkyl chain length on soil Cd desorption was studied using nonionic surfactants of polyethylene oxide (PEO) of PEO chain lengths of 7.5 (Triton X-114), 9.5 (Triton X-100), 30 (Triton X-305), or 40 units (Triton X-405) in combination with the I- ligand. Triplicate 1 g soil samples were equilibrated with 15 ml of surfactant-ligand mixture, at concentrations of 0.025, 0.50 or 0.10, and 0.0, 0.168 or 0.336 mol/l, respectively. After shaking the samples for 24 h, the supernatant fraction was analyzed for Cd content to determine the percent of Cd desorbed from the soil. After five successive washings, 53%, 40% and 25% of Cd had been desorbed by 0.025, 0.050 or 0.10 mol/l of Triton X-114, respectively, in the presence of 0.336 mol/l of I-, whereas with the same conditions, Triton X-100 desorbed 61%, 57% and 56% Cd and either Triton X-305 or Triton X-405 desorbed 51, 40 and 14 to 16% Cd. The most efficient Cd desorption was obtained using 0.025 mol/l Triton X-100 in admixture with 0.336 mol/l I-. Increased surfactant concentration was detrimental to Cd desorption consistent with a process that blocked ligand access to the soil particle surface. After 5 washings,the cumulative cadmium desorption decreased with increasing surfactant alkyl chain length, indicating that the metal-ligand complexes are preferably stabilized by the micelles' hydrophobic octyl phenyl (OP) group rather than by the hydrophilic PEO group. In the absence of ligand, the surfactants alone desorbed less than 1% Cd from the contaminated soil, suggesting that the ligand, rather than the surfactant, extracts the metal, to be subsequently stabilized within the surfactant micelles.

Cadmium↗

PubMed2004

Simultaneous soil Cd and PCB decontamination using a surfactant/ligand solution.

The simultaneous desorption of Cd and PCBs, from a contaminated soil, was investigated using a surfactant/ligand solution. The test surfactants were combinations of a nonionic surfactant [polyethylene oxide (PEO) of chain length 7.5 (Triton X-114), 9.5 (Triton X-100), 30 (Triton X-305), or 40 units (Triton X-405)], with iodide (I-). Triplicate 1 g soil samples were equilibrated, during 24h, with 15 mL of surfactant/ligand solution, at 0.025 or 0.50 and 0.0, 0.168, or 0.336 mol L(-1), respectively. The supernatant fraction was then separated from the particulates by centrifugation and analyzed for Cd to determine Cd desorption efficiency. After five consecutive washings, the treated soil samples were analyzed for PCB content to determine the desorption efficiency of this class of toxicant. Desorption of Cd increased with both increasing ligand concentration and decreasing surfactant chain length and concentration. The maximum Cd desorption efficiency (61%), was obtained with Triton X-100 at 0.025 mol L(-1), in the presence of I at 0.336 mol L(-1). After 5 successive washings, virtually quantitative PCB desorption (below limits of detection for tetra-, penta-, and hexachloro biphenyl compounds) had been achieved with most of surfactant/ligand combinations. Maximum desorption efficiency was achieved using either shorter chain length surfactant (n = 7.5 or 9.5) in combination with a higher ligand concentration, or using longer chain length surfactants (n = 30 and 40) with a lower ligand concentration. Thus, heavy metals and PCBs can be desorbed simultaneously from a contaminated soil with the same washing reagents, namely a surfactant-ligand combination. The optimum surfactant-ligand combination for the simultaneous desorption of both heavy metals and PCBs was a short chain length (n = 7.5 or 9.5) surfactant at low concentration admixed with 0.336 mol L(-1) I-.

Adsorption↗

PubMed2003

Characterization of DNA adducts from lung tissue of asphalt fume-exposed mice by nanoflow liquid chromatography quadrupole time-of-flight mass spectrometry.

A bioanalytical method based on nanoflow liquid chromatography coupled to a hybrid quadrupole orthogonal acceleration time-of-flight mass spectrometry was developed to characterize selected polyaromatic hydrocarbon (PAH)-DNA adducts. The collision-induced dissociation of analytes results in characteristic fragmentation patterns that can be utilized to identify the DNA adducts. In the experiment, 32 B6C3F1 mice were exposed daily (4h/day) to asphalt fume in a whole-body inhalation chamber for 10 days; 16 nonexposed mice served as controls. The asphalt fume was generated at 180 degrees C and the concentrations of PAHs in the animal exposure chamber ranged from 152 to 198 mg/m3. The DNA adducts N2-deoxyguanosine-benzo(a)pyrene-7,8-dihydrodiol-9,10-epoxide (N2-dG-BPDE); N6-deoxyadenosine-benzo(a)pyrene-7,8-dihydrodiol-9,10-epoxide (N6-dA-BPDE), and N4-deoxycytidine-benzo(a)pyrene-7,8-dihydrodiol-9,10-epoxide (N4-dC-BPDE) were identified. The concentrations of N2-dG-BPDE, N6-dA-BPDE, and N4-dC-BPDE adducts were determined to be 1.17, 0.97, and 0.68 pmol/mg DNA, respectively, in the lung tissue of exposed mice using the nanoflow technique. The total DNA adducts in exposed lung tissue was determined to be 8.35 pmol/mg DNA by 32P-postlabeling assay. In total, the results indicated that PAH DNA adducts were significantly elevated (p < 0.001) in the lung tissue of asphalt-fume-exposed mice relative to tissue from control animals.

7,8-Dihydro-7,8-dihydroxybenzo(a)pyrene 9,10-oxide↗

PubMed2002

Recycling of complexometric extractants to remediate a soil contaminated with heavy metals.

Equilibrations were performed with complexing reagent(s) to mobilise Cd, Cu, Mn, Ni, Pb and Zn from a contaminated urban soil. The metal-laden aqueous extract was treated with zero-valent magnesium (Mg0) or bimetallic mixture (Pd0/Mg0 or Ag0/Mg0) to precipitate the heavy metals from solution while liberating the chelating reagent(s). Post precipitation, the pH of aqueous supernatant fraction was readjusted to approximately 5 and the solution was re-combined with the soil particulates to extract more heavy metal pollutants. A sparing quantity of EDTA (10 mmoles) mobilised 32-54% of the 5 mmoles of heavy-metals from the soil with three cycles but only 0.1% of the iron was removed. Three successive extractions with a mixture of complexing reagents (3 mmoles), 1:1 EDTA plus HEDC [bis-(2-hydroxyethyl)-dithiocarbamate], mobilised approximately 49% of the Pb, approximately 18% of the Zn and approximately 19% of the Mn burden but only 7% of the Cu, and 1% of the Fe from this soil. An appreciable fraction of the mobilised Pb and Cu and a portion of the Zn was cemented to the surfaces of the excess magnesium whereas virtually all of the Fe and Mn was removed from solution as insoluble hydroxides.

Biological Availability↗

PubMed2002

Dechlorination of pentachlorophenol in supercritical carbon dioxide with zero-valent palladium-magnesium bimetallic mixture.

A stream of substrate pentachlorophenol [PCP, 5 mg min(-1) in water-methanol (1 + 4, v/v)] was merged with 1.5 ml min(-1) of supercritical carbon dioxide (scCO2) and delivered to a reactor column (25 cm x 1 cm) of zero-valent palladium-magnesium mixture. The resulting dechlorinations, although very efficient, were not quantitative. For continuous operation at 400 degrees C for 6 h, phenol was the principal product, with lesser quantities of methylated products and only traces of chlorinated products (principally monochlorinated species). PCP deoxygenation was not observed and ring methylation was decreased relative to analogous reactions in hydroxylic organic solvent. With time, the reactor column slowly lost dechlorination activity. Reducing the loading of Pd0 on Mg0 from 2% to 1% (w/w) apparently did not change the course of the reaction; however, the dechlorination capacity was decreased correspondingly. None the less, over 6 h or 5 h of continued operation, the dechlorination efficiency was 0.995 for the 2% (w/w) loading of Pd0 on Mg0 and 0.984 for the 1% (w/w) loading.

Carbon Dioxide↗