Equilibrium Porewater Measurement of PCBs and PAHs Using Direct Water Extraction and Comparison with Passive Sampling.

The freely dissolved concentration of hydrophobic pollutants in sediment porewater (Cpw) is a critical driver for exposure to aquatic organisms, bioaccumulation, toxicity, and flux across interfaces. In this research, we compared direct porewater extraction and passive sampling for Cpw measurements of a range of PCBs and PAHs in field-collected sediments. The direct water extraction method provided accurate quantification of Cpw for low to moderately hydrophobic PCB and PAH compounds (log Kow < 6.5) that compared well with independent measurements performed using four passive sampling methods. Direct water extraction was adequate to assess narcosis toxicity of PAHs to benthic organisms that is driven by the concentrations of low to moderately hydrophobic PAHs (naphthalene to chrysene), even for a hypothetical sediment that had a tenth of the PAH concentrations of the study sediments and was assessed to be nontoxic. Prediction of PCB bioaccumulation in benthic organisms agreed within 50% for all measurement methods, but it was apparent that for less contaminated sediments, the direct water extraction method would likely have detection limit challenges, especially for the strongly hydrophobic PCBs. To address the uncertainty of the Cpw measurement of the strongly hydrophobic compounds and naphthalene, a new extrapolation approach is demonstrated that can be applicable for both direct water extraction and passive sampling methods.

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.

Bioavailability assessment in activated carbon treated coastal sediment with in situ and ex situ porewater measurements.

Passive sampling and bioaccumulation assessments were used to evaluate the performance of activated carbon (AC) remediation of polychlorinated biphenyl (PCB) contaminated sediment offshore in Parcel F of the former Hunters Point Naval Shipyard (HPNS) (San Francisco, California). Two different composite AC materials, AquaGate+PAC™ (86 tons) and SediMite™ (24 tons) were placed on the sediment surface covering an area of 3200 m2. PCB tissue concentrations in the clam Macoma nasuta were reduced 75 to 80% in pilot amendment areas after 8 months and 84-87% in non-lipid normalized tissues after 14 months during in situ monitoring, confirming the effectiveness of the AC at reducing bioavailability of the PCBs. Polydimethylsiloxane (PDMS) passive samplers were applied to evaluate and monitor freely dissolved concentrations (Cfree) of PCBs in sediment porewater before AC placement (i.e., during baseline) and at 8 months, 14 months and 26 months following placement. Although AC composite materials were placed only at the surface, 80% reductions were observed to a depth of 16 cm after 8 months and up to 26 cm after 26 months in AquaGate+PAC treatment area. Total PCB porewater concentrations in surface sediments (1-6 cm) were reduced 89 and 91% in the AquaGate+PAC and SediMite areas during final sampling. Ex situ passive sampling showed porewater concentrations 2-5 times larger than in situ measurements due to the absence of hyporheic exchange in laboratory measurements and near equilibration between sediment and porewater. Estimated post placement ex situ porewater concentrations were more consistent with a model of bioaccumulation using the octanol-water partition coefficient (KOW) as a bioaccumulation factor leading to a hypothesis that the bioaccumulation factor in the deposit feeding clam is better estimated by equilibrium ex situ porewater measurements.

Green synthesis of gold nanoparticles using aspartame and their catalytic activity for p-nitrophenol reduction.

We demonstrated a facile and environmental-friendly approach to form gold nanoparticles through the reduction of HAuCl4 by aspartame. The single-crystalline structure was illustrated by transmission electron microscopy (TEM) and X-ray diffraction (XRD). The energy-dispersive X-ray spectroscopy (EDS) and Fourier transform infrared (FTIR) results indicated that aspartame played a pivotal role in the reduction and stabilization of the gold crystals. The crystals were stabilized through the successive hydrogen-bonding network constructed between the water and aspartame molecules. Additionally, gold nanoparticles synthesized through aspartame were shown to have good catalytic activity for the reduction of p-nitrophenol to p-aminophenol in the presence of NaBH4.