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Molecular diffusion across the sediment-water interface, as one of the key geochemical processes, dictates whether a sediment is a source or sink of chemicals, providing useful data in designing remedial actions. Despite ample previous efforts in quantifying sediment-water diffusion fluxes, the resulting methods are largely unsatisfactory. Herein, we introduce a novel passive sampling device capable of measuring vertical profiles of chemical concentrations near the sediment-water interface, from which diffusion fluxes can be calculated based on a model that we developed. In laboratory testing, diffusion fluxes (0.032-310 ng m(-2) d(-1)) of dichlorodiphenyltrichloroethane and its metabolites obtained from the present sampling device were consistent with those (0.38-610 ng m(-2) d(-1)) determined by using a conventional active sampling method, solid-phase extraction/liquid-liquid extraction. Field deployment of the sampling device yielded individual diffusion fluxes of p,p'-DDD, p,p'-DDE, p,p'-DDMU, o,p'-DDMU, p,p'-DDNU, and p,p'-DBP in the range of 5.9-150 ng m(-2) d(-1), which were comparable to those (5.5-85 ng m(-2) d(-1)) obtained with a benthic chamber. Moreover, diffusion fluxes of p,p'-DDT and o,p'-DDT obtained with the sampling device were negative; i.e., the sediment is acting as a sink for these chemicals, while that could not be found using the benthic chamber. Thus, the passive sampling device can provide better information about the movement of chemicals through the sediment and overlying water for the choice of remedial strategies.

Solid-phase microextraction (SPME) has often been used to estimate the freely dissolved concentration ( Cfree) of organic contaminants in sediments. A significant limitation in the application of SPME for Cfree measurement is the requirement for attaining equilibrium partition, which is often difficult for strongly hydrophobic compounds such as DDT. A method was developed using SPME with stable isotope-labeled analogues as performance reference compounds (PRCs) to measure Cfree of DDT and metabolites (DDTs) in marine sediments. Six 13C-labeled or deuterated PRCs were impregnated into polydimethylsiloxane (PDMS) fiber before use. Desorption of PRCs from PDMS fibers and absorption of DDTs from sediment were isotropic in a range of sediments evaluated ex situ under well-mixed conditions. When applied to a historically contaminated marine sediment from a Superfund site, the PRC-SPME method yielded Cfree values identical to those found by using a conventional equilibrium SPME approach (Eq-SPME), wherease the time for mixing was reduced from 9 d to only 9 h. The PRC-SPME method was further evaluated against bioaccumulation of DDTs by Neanthes arenaceodentata in the contaminated sediment with or without amendment of activated carbon or sand. Strong correlations were consistently found between the derived equilibrium concentrations on the fiber and lipid-normalized tissue residues for DDTs in the worms. Results from the present study clearly demonstrated the feasibility of coupling PRCs with SPME sampling to greatly shorten sampling time, thus affording much improved flexibility in the use of SPME for bioavailability evaluation. Environ Toxicol Chem 2013;32:1946-1953. © 2013 SETAC [ABSTRACT FROM AUTHOR]

A passive water sampler with low-density polyethylene (LDPE) as the sorbent phase was built and field-tested for sensing freely dissolved concentrations of hydrophobic organic compounds (HOCs) in fresh and coastal water. Based on the measured LDPE-water partition coefficients ( Kpew) of 12 polycyclic aromatic hydrocarbons (PAHs) and dichlorodiphenyltrichloroethane (DDT) and its seven metabolites, the detection limits with the passive sampler containing 10-g LDPE ranged from 0.04 to 56.9 pg/L in the equilibrium sampling mode. Furthermore, the utility of the passive sampler in measuring dissolved HOC concentrations in open waters was examined through a comparison with solid-phase extraction combined with liquid-liquid extraction (SPE-LLE) and poly(dimethyl)siloxane (PDMS) coated fiber samplers. The total concentrations of PAHs (3.8-16 ng/L) obtained by the passive sampler were lower than those (87.7-115.5 ng/L) obtained through SPE-LLE. This large difference was probably attributable to slower water exchange in and out of the passive sampler as time progressed because of blockage by algae in eutrophia reservoirs and high dissolved organic carbon contents resulting in higher-than-expected PAH concentrations by SPE-LLE. Furthermore, the concentrations and compositional profiles of DDXs (sum of p,p′-DDT, p,p′-DDD, p,p′-DDE, o,p′-DDT, o,p′-DDD, o,p′-DDE, and p,p′-DDMU) at site A obtained by the passive sampler agreed with the results obtained with the PDMS-coated fibers, suggesting that the passive sampler was able to reasonably quantify dissolved HOCs in seawater. Environ. Toxicol. Chem. 2012; 31: 1012-1018. © 2012 SETAC [ABSTRACT FROM AUTHOR]

Abstract: With compiled and analyzed information about recent advances in passive sampling techniques for sediment porewater, we discuss common quantitation methods (equilibrium and kinetic diffusion-controlled sampling), effects of temperature and salinity on passive sampling, and benefits and drawbacks of currently available passive samplers based on the principles of solid-phase microextraction. The results show that the in-fiber standardization technique, which is kinetic diffusion-controlled, could shorten sampling time and obtain accurate results using isotopically-labeled reference compounds. Another quantitative method, time-weighted average sampling, may be viable for simultaneously measuring all analytes in sediment porewater, as it is more effective with respect to cost and time. In addition, the effects of temperature and salinity on passive sampling should be quantified in field applications. Currently available passive samplers (e.g., employing polymer-coated fibers and low-density polyethylene sheets) can sense hydrophobic organic chemicals (HOCs) in sediment porewater, but the small capacity and the inflexibility of polymer-coated fibers need to be further improved, while better physical protection of polyethylene devices, particularly when they are deployed under rough conditions, should be carefully considered. In conclusion, passive samplers for in-situ measurement of dissolved HOCs in sediment porewater should be combined with a suitable quantitative method and calibration for the effects of temperature and salinity. [Copyright &y& Elsevier]

Abstract: A conventional solid-phase microextraction (SPME) method combined with liquid–liquid extraction was applied under equilibrium and nonequilibrium conditions to determine the partition coefficients (K doc) of 25 polychlorinated biphenyl congeners (PCBs) between Sigma–Aldrich humic acid (HA) and water. The values of log K doc determined with equilibrium SPME were linearly correlated with the logarithm of the octanol–water partition coefficients (K ow) for PCB congeners at log K ow <∼7.2, but the trends were disrupted for log K ow from ∼7.2 to 8.18. In addition, short-term (5min to 4 days) and long-term (5–44 days) uptake profiles of PCBs were established, from which a pseudo-equilibrium for sorption of PCBs was revealed at ∼4 days of extraction. To understand this phenomenon, the uptake profiles were fitted with two equations (one equation is often used for pure water samples and the other one is applicable for samples containing complex matrices) derived from a first-order kinetics model. Subsequently, K doc values obtained through kinetic approaches were compared with those acquired from equilibrium SPME. The comparison of K doc values indicated that the pseudo-equilibrium was caused by the slow desorption of PCBs from HA rather than the biphasic desorption mechanism. [Copyright &y& Elsevier]