Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility

Reible, Danny D.; Lotufo, Gui; Skwarski, Alison; Lampert, David J.; Lu, Xiaofan

doi:10.21236/ada495607

Cited by 6 publications

(12 citation statements)

References 12 publications

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“…The resulting correlation and confidence intervals, applicable to high molecular weight PAHs and PCBs, was given by Equation (3). Selected measurements of PCB fiber water partition coefficients gave results within the error bounds of this relationship 26 . Because of the availability of this relationship for highly hydrophobic compounds, the focus was on extending this correlation to moderate to low hydrophobicity compounds with K ow ≤5-5.5.…”

Section: Demonstration Design and Resultsmentioning

confidence: 96%

Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility

Reible¹,

Lotufo²

2012

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Standard Form 298 (Rev. 8/98) REPORT DOCUMENTATION PAGEPrescribed by ANSI Std. Z39.18 Form Approved OMB No. 0704-0188The public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing the burden, to the Department of Defense, Executive Services and Communications Directorate (0704-0188). Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. The goal of the project was to develop and standardize a procedure using field deployable solid phase microextraction (SPME) for the measurement of freely-dissolved porewater concentrations of hydrophobic organics and demonstrate the relationship of these measurements to contaminant flux, bioavailability and bioaccumulation. PLEASE DO NOT RETURN YOUR FORM 139Danny Reible 512-471-4642Reset ii EXECUTIVE SUMMARY OBJECTIVES OF THE DEMONSTRATIONThe goal of the project was to develop and standardize a procedure using field deployable solid phase microextraction (SPME) for the measurement of freely-dissolved porewater concentrations of hydrophobic organics and demonstrate the relationship of these measurements to contaminant flux, bioavailability and bioaccumulation.Specific objectives of the PDMS technology for hydrophobic organic compounds include:Determination of mobile and available contaminants in sediments Assessment of bioaccumulation potential in benthic organisms Assessment of vertical chemical profiles in surficial sediments and sediment capsThe work was conducted in sediments both in laboratory and field testing. Laboratory testing allows sediments to be collected and tested in the laboratory, avoiding problematic field deployments where placement and retrieval is too difficult or costly. This testing also allows coupling of availability measurements with laboratory bioassays under controlled conditions avoiding the difficulties and variability of field bioassays. The field testing allows determination of availability and cap performance under conditions that might not be reproducible in the laboratory. All porewater measurements herein were measured in-situ (i.e. in sediments whether field or lab) and require no porewater separation from the sediments prior to analysis. TECHNOLOGY DESCRIPTIONIn-situ solid-phase microextraction (SPME) is a passive sampling approach for measuring hydrophobic organic contaminants in porewater and involves the insertion of a polymer sorbent into the sediments, withdrawal after a period of time, preferably after achievement of equilibrium, and measuring the contaminants sorbed to the polymer. The contaminant conc...

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Section: Demonstration Design and Resultsmentioning

confidence: 96%

Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility

Reible¹,

Lotufo²

2012

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“…Passive sampling-derived C free correlates more closely with contaminant uptake and toxicity in benthic organisms than do total solid-phase concentrations (C total ) or other commonly implemented partitioning model estimates and thus is a better indicator of bioavailability and risk (Hawthorne, Azzolina et al 2007;Jonker et al 2007;Lu et al 2011;Lydy et al 2014). Because it provides a quantitative measurement of freely dissolved concentrations, PSMderived C free also is useful in modeling the flux of contaminants through the sediment and into surficial waters (Reible and Lotufo 2012;Lampert et al 2013; Thomas et al 2014). The use of PSMs has grown rapidly in both academic (Ghosh et al 2014;Lydy et al 2014) and regulatory (USEPA 2005(USEPA , 2012a(USEPA , 2012b settings over the past 10 to 15 y with a focus primarily on assessing heavily contaminated sediment.…”

Section: Introductionmentioning

confidence: 99%

The utility of solid‐phase microextraction in evaluating polycyclic aromatic hydrocarbon bioavailability during habitat restoration with dredged material at moderately contaminated sites

Brennan

Johnson

2017

Integr Envir Assess & Manag

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The over- or underprediction of risk in moderately contaminated sediments can have a large impact on the nature of applied management strategies given that concentrations border on being toxic or not toxic. Project managers should give significant consideration as to how moderate levels of contaminants in native sediments and dredged material used for restoration will impact recovery of habitat. Total solid-phase (C ) and porewater (C ) polycyclic aromatic hydrocarbons (PAHs) were quantified in native sediments and dredged material to determine if the predictions of risk from C are consistent with those based on C . The sediment matrix phase in which PAHs were quantified resulted in disparate conclusions regarding the predicted reduction in contamination following restoration. Total solid-phase PAH concentrations suggested a significant decrease following restoration, whereas little to no change was observed in measured C . Risk metrics based on C gave inconclusive estimates for toxicity, whereas measured C suggested toxicity is unlikely, a conclusion consistent with toxicity testing. The incorporation of black carbon (BC) into model estimates for C gave predictions more consistent with measured C , suggesting that geochemical conditions (especially BC) play an important part in predicting toxicity at moderately contaminated sites. In addition to the use of C in toxicity evaluation, in-situ C measurements provided a constraint on diffusive PAH loads from sediment relative to ongoing stream loads. If passive sampling had been employed during the sampling designs and site evaluations, the costs of toxicity testing would not have been incurred, given that C suggested little to no toxicity. The results from the project highlight the benefits to be gained by moving beyond inconclusive, screening-level C metrics and implementing more sensitive and accurate C metrics in assessments of risk in moderately contaminated sediments. Integr Environ Assess Manag 2018;14:212-223. © 2017 SETAC.

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“…Because of the differences in the compound properties for the PRC and the target analyte, correction is needed to calculate the fractional approach to equilibrium for the target analyte (C(t)/C(ss)) from the fractional PRC dissipation (1-C PRC (t)/C PRC0 ) at time t. In addition, PRC correction becomes difficult if sorption in the surrounding media is concentration dependent. Several approaches for the calibration using PRC data have been suggested (Huckins et al 2006;Tomaszewski and Luthy 2008;Fernandez et al 2009b;Reible and Lotufo 2012).…”

Section: Calibration Of Polymer Exchange Kinetics (K E )mentioning

confidence: 99%

“…Even for the most hydrophobic contaminants such as PCBs and HMW PAHs, this exposure time yields (near) equilibrium concentrations (Maruya et al 2009;Hawthorne et al 2011). Using vials and SPME fibers containing a thin PDMS coating (e.g., 10 mm PDMS), full equilibration can be achieved within a (2001); Hawthorne et al (2009Hawthorne et al ( , 2011 Oil (GC-FID) Hexane/acetone 6 Jonker (2011, 2012) PE PCBs, PAHs, DDTs, PBDEs, triclosan Dichloromethane, hexane, acetone 24 Fernandez et al (2009aFernandez et al ( , 2009bFernandez et al ( , 2012; Perron et al (2009Perron et al ( , 2013aPerron et al ( , 2013b PDMS-SPME PAHs (HPLC) Methanol, water, acetonitrile 3 Jonker (2009, 2012) Oil (GC-FID) Heptane 3 Jonker (2011, 2012) PAHs, PCBs, other semivolatiles Thermal desorption 0.5 ASTM (2007); Reible and Lotufo (2012) Silicone rubber PAHs, PCBs Ethyl acetate 100 Smedes et al (2009) PDMS-SPME ¼ polydimethylsiloxane-solid phase microextraction; PE ¼ polyethylene; POM ¼ polyoxymethylene.…”

Section: Ex Situ ("Laboratory") Exposuresmentioning

confidence: 99%

“…Although PRCs have proven successful in water-only exposures (Huckins et al 2002(Huckins et al , 2006Fernandez et al 2012;Perron et al 2013aPerron et al , 2013b, this approach in static sediment-water systems is still being developed (Tomaszewski and Luthy 2008;Fernandez et al 2009aFernandez et al , 2009bFernandez et al , 2012Gschwend et al 2011;USEPA 2012aUSEPA , 2012b. One study with POM was recently performed successfully by Oen et al (2011), but studies on the utility of PRCs for use with PDMS and POM have been limited so far (Reible and Lotufo 2012). Alternatively, equilibrium in the field can be established by performing 2 different thickness samplers (Reible and Lotufo 2012) or by time series deployment (Tomaszewski and Luthy 2008), staggering the removal schedule of individual samplers over a period within which the establishment of equilibrium can be expected.…”

Section: Ex Situ ("Laboratory") Exposuresmentioning

confidence: 99%

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

Ghosh

Driscoll

Burgess

et al. 2014

Integr Environ Assess Manag

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129

164

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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. © 2014 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of SETAC.

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Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility

Cited by 6 publications

References 12 publications

Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility

Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility

The utility of solid‐phase microextraction in evaluating polycyclic aromatic hydrocarbon bioavailability during habitat restoration with dredged material at moderately contaminated sites

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

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