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Open Access Publications from the University of California

Scholarly Works (7 results)

  • Article
  • Peer Reviewed
UC Riverside Previously Published Works (2014)
Polybrominated diphenyl ethers (PBDEs) are widely found in sediments, especially congeners from the penta-BDE formula. Due to their strong affinity for black carbon (BC), bioavailability of PBDEs may be decreased in BC-amended sediments. In this study, we used a matrix-SPME method to measure the freely dissolved concentration (Cfree) of PBDEs as a parameter of their potential bioavailability and evaluated the differences among biochar, charcoal, and activated carbon. Activated carbon displayed a substantially greater sequestration capacity than biochar or charcoal. At 1% amendment rate in sediment with low organic carbon (OC) content (0.12%), Cfree of six PBDEs was reduced by 47.5-78.0%, 47.3-77.5%, and 94.1-98.3% with biochar, charcoal, and activated carbon, respectively, while the sequestration was more limited in sediment with high OC content (0.87%). Therefore, it is important to consider the type and properties of the BC and the sediment in BC-based remediation or mitigation.
    Cover page: Comparing black carbon types in sequestering polybrominated diphenyl ethers (PBDEs) in sediments
    • Thesis
    • Peer Reviewed
    UC Riverside Electronic Theses and Dissertations (2014)

    Due to high affinity for organic carbon phase, hydrophobic organic contaminants (HOCs) preferentially deposit in bed sediments in surface aquatic systems. Consequently, many contemporary sediment contaminants are HOCs, including DDTs, PCBs, and PBDEs. However, their accumulation potential and toxicity to benthic organisms in sediments are regulated by bioavailability, rather than bulk chemical concentrations. The overall purpose of the current project was to develop and apply chemically-based methods to explore bioavailability of HOCs in sediments, and help improve the assessment of their potential ecotoxicological risks and sometimes human health effects in the environment.

    A solid phase microextraction (SPME) method using disposable polydimethylsiloxane (PDMS) fibers was developed for measuring the phase distribution of flame retardant PBDEs in sediments. Results showed that PBDEs were predominantly sorbed to the sediment phase, with freely dissolved concentration (Cfree) only accounted for < 0.012% of the total chemical mass and < 0.43% of the dissolved mass. Addition of black carbon further reduced bioavailability (or Cfree) of HOCs as indicated by the matrix-SPME method. At 1% amendment rate in a sediment with low organic carbon (0.12%) content, Cfree of selected PBDEs was reduced by 47.5&ndash78.0%, 47.3&ndash77.5%, and 94.1&ndash98.3% with biochar, charcoal, and activated carbon, respectively. To overcome the shortcomings of current measurement methods, an isotope dilution method (IDM) was developed and applied for bioavailability prediction of legacy HOCs (e.g., DDT and its metabolites, PCBs) in historically-contaminated sediments from the Palos Verdes Superfund site. The IDM-based accessible concentration was shown to correlate closely with tissue residues in the exposed marine benthic polychaete Neanthes arenaceodentata (R2=0.84&ndash0.94). Bioavailability measurements from the SPME, IDM and Tenax methods were compared in amendment-based remediation. After normalizing over the unamended sediments, significant linear correlations (R2 >0.90, p <0.01, slopes=1.00&ndash1.09) were found between these methods, suggesting they are interchangeable or complementary for evaluating remediation efficiency or progress.

    Overall, the bioavailability estimation methods or their specific applications developed from this project will improve understanding environmental fate of HOCs and their potential toxicity to such organisms as the sediment-dwelling invertebrates. The developed methods may be readily adoptable for other HOCs as well as other matrices (e.g., soil).

      Cover page: Exploring Bioavailability of Hydrophobic Organic Contaminants in Sediments
      • Article
      • Peer Reviewed
      UC Riverside Previously Published Works (2014)
      Many cases of severe environmental contamination arise from historical episodes, where recalcitrant contaminants have resided in the environment for a prolonged time, leading to potentially decreased bioavailability. Use of bioavailable concentrations over bulk chemical levels improves risk assessment and may play a critical role in determining the need for remediation or assessing the effectiveness of risk mitigation operations. In this study, we applied the principle of isotope dilution to quantify bioaccessibility of legacy contaminants DDT and PCBs in marine sediments from a Superfund site. After addition of 13C or deuterated analogues to a sediment sample, the isotope dilution reached a steady state within 24 h of mixing. At the steady state, the accessible fraction (E) derived by the isotope dilution method (IDM) ranged from 0.28 to 0.89 and was substantially smaller than 1 for most compounds, indicating reduced availability of the extensively aged residues. A strong linear relationship (R2=0.86) was found between E and the sum of rapid (Fr) and slow (Fs) desorption fractions determined by sequential Tenax desorption. The IDM-derived accessible concentration (Ce) was further shown to correlate closely with tissue residue in the marine benthic polychaete Neanthes arenaceodentata exposed in the same sediments. As shown in this study, the IDM approach involves only a few simple steps and may be readily adopted in laboratories equipped with mass spectrometers. This novel method is expected to be especially useful for historically contaminated sediments or soils, for which contaminant bioavailability may have changed significantly due to aging and other sequestration processes.
        Cover page: Use of isotope dilution method to predict bioavailability of organic pollutants in historically contaminated sediments.
        • Article
        • Peer Reviewed
        UC Riverside Previously Published Works (2014)
        Many cases of severe environmental contamination arise from historical episodes, where recalcitrant contaminants have resided in the environment for a prolonged time, leading to potentially decreased bioavailability. Use of bioavailable concentrations over bulk chemical levels improves risk assessment and may play a critical role in determining the need for remediation or assessing the effectiveness of risk mitigation operations. In this study, we applied the principle of isotope dilution to quantify bioaccessibility of legacy contaminants DDT and PCBs in marine sediments from a Superfund site. After addition of 13C or deuterated analogues to a sediment sample, the isotope dilution reached a steady state within 24 h of mixing. At the steady state, the accessible fraction (E) derived by the isotope dilution method (IDM) ranged from 0.28 to 0.89 and was substantially smaller than 1 for most compounds, indicating reduced availability of the extensively aged residues. A strong linear relationship (R2=0.86) was found between E and the sum of rapid (Fr) and slow (Fs) desorption fractions determined by sequential Tenax desorption. The IDM-derived accessible concentration (Ce) was further shown to correlate closely with tissue residue in the marine benthic polychaete Neanthes arenaceodentata exposed in the same sediments. As shown in this study, the IDM approach involves only a few simple steps and may be readily adopted in laboratories equipped with mass spectrometers. This novel method is expected to be especially useful for historically contaminated sediments or soils, for which contaminant bioavailability may have changed significantly due to aging and other sequestration processes.
          Cover page: Use of Isotope Dilution Method To Predict Bioavailability of Organic Pollutants in Historically Contaminated Sediments
          • Article
          • Peer Reviewed
          UC Riverside Previously Published Works (2016)
          An overlooked issue for field application of in situ performance reference compound (PRC) calibration methods is the validity of the assumption that both the sorption of a target compound and desorption of its corresponding PRC follow the first-order kinetics with the same rate constants under stagnant conditions. In the present study, disposable polydimethylsiloxane fibers of 2 sizes (7 and 35 µm) impregnated with 8 (13) C-labeled or deuterated PRCs were statically deployed into different marine sediments, from which the kinetics for sorption of the target compounds and desorption of the PRCs were characterized. Nonsymmetrical profiles were observed for exchange of the target analytes and their corresponding PRCs in sediment under stagnant conditions. The hysteretic desorption of PRCs in the kinetic regime may be ascribed to the low chemical potential between the fiber and sediment porewater, which reflects the inability of water molecules to rapidly diffuse through sediment to solvate the PRCs in the aqueous layer around the fiber surface. A moderate correlation (r = 0.77 and r = 0.57, p < 0.05 for both regressions) between the PRC-calibrated equilibrium concentrations of 1,1-dichloro-2,2-bis-(chlorophenyl) ethylene (p,p'-DDE) and polychlorinated biphenyl (PCB)-153 and the lipid normalized levels in worms (Neanthes arenaceodentata) was obtained in co-exposure tests under simulating field conditions, probably resulting from slightly overestimated bioavailability because of the hysteretic desorption of PRCs and toxic effects. Environ Toxicol Chem 2016;35:1978-1985. © 2015 SETAC.
            Cover page: Isotopic exchange on solid‐phase micro extraction fiber in sediment under stagnant conditions: Implications for field application of performance reference compound calibration
            • Article
            • Peer Reviewed
            UC Riverside Previously Published Works (2016)
            High concentrations of DDT and metabolites (ΣDDT) have been detected in sediment and the demersal flatfish hornyhead turbot (Pleuronichtys verticalis) collected from Palos Verdes (PV), California, USA, a site contaminated with over 100 metric tons of DDT throughout 1960s-70s. This study was conducted to assess the transfer of ΣDDT from PV-sediment into polychaetes (Neanthes arenaceodentata) and hornyhead turbot, and to investigate if the responses in turbots from two different laboratory exposures mimic those in turbots caught in PV (PV-turbot). Turbot fed PV-sediment-contaminated polychaete for 7 days had liver concentrations of ΣDDT similar to PV-turbot. After 28 days, ΣDDT also accumulated in livers of turbot gavaged with a ΣDDT mixture. In vitro cell bioassays indicated significant increases of 17β-estradiol equivalents (EEQ) in turbot bile extracts as compared to the control in the 7-day study. These responses corresponded to those measured in PV-fish. Glucocorticoid receptor (GR), anti-androgen receptor (anti-AR), estrogen receptor (ER) or aryl hydrocarbon receptor (AhR) activities were also observed in extracts of PV-sediment, and PV-sediment-exposed worm. Anti-AR, AhR and GR activities were significantly higher in PV-sediment than reference sediment (San Diego, SD). Higher transcripts of hepatic VTG, ERα and ERβ were found in PV-turbot than SD-turbot, but were unaltered in fish exposed to sediment-contaminated worms for the 7-day study. In contrast, liver extracts from the 28-day treatment of ΣDDT showed lower EEQ but similar hepatic VTG and ERβ transcripts relative to those of PV-turbot. These data indicated that trophic transfer of sediment-associated DDT in 7-day exposures corresponded to field measurements of DDT residues and in vitro ER bioactivities, but failed to mimic in vivo biological effects observed in field fish. In contrast, treatment with ΣDDT alone for 28 days mimicked in vivo biological effects of DDTs in PV fish, but did not correspond to liver concentrations or in vitro bioactivities.
              Cover page: Trophic transfer and effects of DDT in male hornyhead turbot (Pleuronichthys verticalis) from Palos Verdes Superfund site, CA (USA) and comparisons to field monitoring
              • Article
              • Peer Reviewed
              UC Davis Previously Published Works (2015)
              Monilinia fructicola is a devastating pathogen on stone fruits, causing blossom blight and fruit rot. Little is known about pathogenic mechanisms in M. fructicola and related Monilinia species. In this study, five endopolygalacturonase (endo-PG) genes were cloned and functionally characterized in M. fructicola. Quantitative reverse-transcriptase PCR (qRT-PCR) revealed that the five MfPG genes are differentially expressed during pathogenesis and in culture under various pH regimes and carbon and nitrogen sources. MfPG1 encodes the major endo-PG and is expressed to significantly higher levels compared to the other four MfPGs in culture and in planta. MfPG1 function during pathogenesis was evaluated by examining the disease phenotypes and gene expression patterns in M. fructicola MfPG1-overexpressing strains and in strains carrying the β-glucuronidase (GUS) reporter gene fused with MfPG1 (MfPG1-GUS). The MFPG1-GUS reporter was expressed in situ in conidia and hyphae following inoculation of flower petals, and qRT-PCR analysis confirmed MfPG1 expression during pathogenesis. MfPG1-overexpressing strains produced smaller lesions and higher levels of reactive oxygen species (ROS) on the petals of peach and rose flowers than the wild-type strain, suggesting that MfPG1 affecting fungal virulence might be in part resulted from the increase of ROS in the Prunus-M. fructicola interactions.
                Cover page: Expression of Five Endopolygalacturonase Genes and Demonstration that MfPG1 Overexpression Diminishes Virulence in the Brown Rot Pathogen Monilinia fructicola
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