Interlaboratory Study of Polyethylene and Polydimethylsiloxane Polymeric Samplers for Ex Situ Measurement of Freely Dissolved Hydrophobic Organic Compounds in Sediment Porewater.

We evaluated the precision and accuracy of multilaboratory measurements for determining freely dissolved concentrations (Cfree ) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in sediment porewater using polydimethylsiloxane (PDMS) and low-density polyethylene (LDPE) polymeric samplers. Four laboratories exposed performance reference compound (PRC) preloaded polymers to actively mixed and static ex situ sediment for approximately 1 month; two laboratories had longer exposures (2 and 3 months). For Cfree results, intralaboratory precision was high for single compounds (coefficient of variation 50% or less), and for most PAHs and PCBs interlaboratory variability was low (magnitude of difference was a factor of 2 or less) across polymers and exposure methods. Variability was higher for the most hydrophobic PAHs and PCBs, which were present at low concentrations and required larger PRC-based corrections, and also for naphthalene, likely due to differential volatilization losses between laboratories. Overall, intra- and interlaboratory variability between methods (PDMS vs. LDPE, actively mixed vs. static exposures) was low. The results that showed Cfree polymer equilibrium was achieved in approximately 1 month during active exposures, suggesting that the use of PRCs may be avoided for ex situ analysis using comparable active exposure; however, such ex situ testing may not reflect field conditions. Polymer-derived Cfree concentrations for most PCBs and PAHs were on average within a factor of 2 compared with concentrations in isolated porewater, which were directly measured by one laboratory; difference factors of up to 6 were observed for naphthalene and the most hydrophobic PAHs and PCBs. The Cfree results were similar for academic and private sector laboratories. The accuracy and precision that we demonstrate for determination of Cfree using polymer sampling are anticipated to increase regulatory acceptance and confidence in use of the method. Environ Toxicol Chem 2022;41:1885-1902. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

Advancing the Use of Passive Sampling in Risk Assessment and Management of Sediments Contaminated with Hydrophobic Organic Chemicals: Results of an International Ex Situ Passive Sampling Interlaboratory Comparison.

This work presents the results of an international interlaboratory comparison on ex situ passive sampling in sediments. The main objectives were to map the state of the science in passively sampling sediments, identify sources of variability, provide recommendations and practical guidance for standardized passive sampling, and advance the use of passive sampling in regulatory decision making by increasing confidence in the use of the technique. The study was performed by a consortium of 11 laboratories and included experiments with 14 passive sampling formats on 3 sediments for 25 target chemicals (PAHs and PCBs). The resulting overall interlaboratory variability was large (a factor of ∼10), but standardization of methods halved this variability. The remaining variability was primarily due to factors not related to passive sampling itself, i.e., sediment heterogeneity and analytical chemistry. Excluding the latter source of variability, by performing all analyses in one laboratory, showed that passive sampling results can have a high precision and a very low intermethod variability (

Positioning activated carbon amendment technologies in a novel framework for sediment management.

Contaminated sediments can pose serious threats to human health and the environment by acting as a source of toxic chemicals. The amendment of contaminated sediments with strong sorbents like activated C (AC) is a rapidly developing strategy to manage contaminated sediments. To date, a great deal of attention has been paid to the technical and ecological features and implications of sediment remediation with AC, although science in this field still is rapidly evolving. This article aims to provide an update on the recent literature on these features, and provides a comparison of sediment remediation with AC to other sediment management options, emphasizing their full-scale application. First, a qualitative overview of advantages of current alternatives to remediate contaminated sediments is presented. Subsequently, AC treatment technology is critically reviewed, including current understanding of the effectiveness and ecological safety for the use of AC in natural systems. Finally, this information is used to provide a novel framework for supporting decisions concerning sediment remediation and beneficial reuse.

Equilibrium and kinetic modeling of contaminant immobilization by activated carbon amended to sediments in the field.

Addition of activated carbons (AC) to polluted sediments and soils is an attractive remediation technique aiming at reducing pore water concentrations of hydrophobic organic contaminants (HOCs). In this study, we present (pseudo-)equilibrium as well as kinetic parameters for sorption of a series of PAHs and PCBs to powdered and granular activated carbons (AC) after three different sediment treatments: sediment mixed with powdered AC (PAC), sediment mixed with granular AC (GAC), and addition of GAC followed by 2 d mixing and subsequent removal ('sediment stripping'). Remediation efficiency was assessed by quantifying fluxes of PAHs towards SPME passive samplers inserted in the sediment top layer, which showed that the efficiency decreased in the order of PAC > GAC stripping > GAC addition. Sorption was very strong to PAC, with Log KAC (L/kg) values up to 10.5. Log KAC values for GAC ranged from 6.3-7.1 and 4.8-6.2 for PAHs and PCBs, respectively. Log KAC values for GAC in the stripped sediment were 7.4-8.6 and 5.8-7.7 for PAH and PCB. Apparent first order adsorption rate constants for GAC (kGAC) in the stripping scenario were calculated with a first-order kinetic model and ranged from 1.6 × 10(-2) (PHE) to 1.7 × 10(-5) d(-1) (InP). Sorption affinity parameters did not change within 9 months post treatment, confirming the longer term effectiveness of AC in field applications for PAC and GAC.