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Graphical abstract Highlights • Crude e-waste recycling was simulated in closed chamber. • Emissions of OPFRs were large in both thermal treatment and open burning. • OPFRs were probably emitted in association with particles. • The abundances of OPFRs were lower in coarse particles than in fine particles. Abstract Organophosphate flame retardants (OPFRs) have been increasingly produced and consumed since the gradual phase-out of polybrominated diphenyl ethers. Primitive recycling of e-waste can be a significant input source of OPFRs to the environment. Thermal treatment and open burning of typical e-wastes were conducted in a closed chamber to examine the emissions and the size distribution patterns of particle-bound OPFRs from these processes. The sum emission factors of OPFRs were 3.70 × 104–3.65 × 105 ng g−1 by thermal treatment and 5.22 × 103–9.27 × 104 ng g−1 by open burning. The output-input mass ratios of OPFRs for plastic casings were 0.030–116 and 0.012–7.1 by thermal treatment and open burning, respectively, and were 0.11–40 and 0.0014–6.7 for printed circuit boards. The size distribution patterns of OPFRs were characterized by one unimodal peak (0.56–1.0 μm) for thermal treatment and bimodal peaks (0.56–1.0 or 1.0–1.8 and 10–18 μm) for open burning. Particle-bound OPFRs appeared to form in affiliation with particles rather than by adsorption or deposition from the gaseous phase to particulate organic matter. With increasing amounts of OPFRs used in a variety of consumer products, the emissions of OPFRs to the environment are expected to increase continuously in the future. [ABSTRACT FROM AUTHOR]

Natural organic matter and grain size are considered as important parameters dictating the transport and fate of organic compounds in sediment. However, increasing evidence suggested that manufactured debris may alter the underlying mechanisms for biogeochemical cycling of organic compounds. To examine this assumption, estuarine sediment and embedded debris were collected from a fishery base in Guangdong Province of South China and analyzed for organophosphorus flame retardants (OPFRs), phthalates (PAEs), organotin compounds (OTs) and dichlorodiphenyltrichloroethanes (DDTs). Coarse-size debris (> 200 μm) were heterogeneously distributed in sediment, and most abundant near the boat maintenance facilities, aquaculture zone and shipping channel. The median concentrations of OPFRs, OTs, PAEs and DDTs in debris were 11 , 0.2, 11 and 3.9 μg g −1 dry sample weight −1 , respectively, 1 to 3 orders of magnitude greater than those in bulk sediment (19, 60, 240 and 570 ng g −1 dry sample weight −1 , respectively). Furthermore, OPFRs, OTs and PAEs were mostly (> 99%) enriched in coarse-size (63–2000 μm) sediment, and there was no significant correlation ( p > 0.05) between the concentrations of OPFRs, OTs and PAEs in bulk and size-fractioned sediment samples and total organic carbon or grain size, similar to the distribution pattern of DDTs reported previously. When distinct debris were removed from the light-density (< 1.7 g cm −3 ) fraction of coarse-size (200–2000 μm) sediment, the concentration levels of OPFRs, OTs, PAEs and DDTs declined by 84%, 59%, 55% and 7%, respectively. Obviously, debris irregularly distributed in sediment can alter the sediment sorption capacity for OPFRs, OTs and PAEs, and thus may undermine the significance of organic matter and grain size to the distribution of organic chemicals in sediment. Finally, commonly used procedures for preparing sediment samples and screening of debris may disturb the grain size distribution or underestimate the abundance of heavy-density debris, resulting in flawed sediment quality assessment. [ABSTRACT FROM AUTHOR]

Recently published literature indicated that dichlorodiphenyltrichloroethane (DDT)-containing antifouling paint flakes were heterogeneously distributed within estuarine sediments. However, the significance of antifouling paint flakes in the fate and transport of DDT compounds and other organic pollutants in estuarine sediment is yet to be adequately addressed. To fill this knowledge gap, estuarine sediment and paint flakes from cabin and boat surfaces were collected from a fishery base in Guangdong Province of South China and analyzed for DDT compounds. Coarse fractioned samples collected from the vicinity of boat maintenance facilities contained appreciable amounts of colorful particles, which were identified as paint flakes by Fourier transform infrared spectroscopy. The highest concentrations of DDXs (sum of DDTs and its metabolites) occurred in the heavy-density (>1.7 g cm −3 ) fraction of coarse-size (200–2000 μm) sediments from near the boat maintenance facilities, suggesting the importance of paint flakes in the distribution pattern of “hot spots” in estuarine sediment. Moreover, the desorption rates of DDT compounds from paint flakes and the heavy-density fraction of coarse-size sediment were both extremely slow. Apparently, unevenly distributed paint flakes in sediment can artificially inflate the sorption capacity of heavy-density sediment for DDT compounds, and therefore can substantially change the environmental fate and behavior of hydrophobic organic chemicals in estuarine sediment. Finally, commonly used source diagnostic indices of DDT compounds were mostly grain-size and density dependent in sediment, as a result of the occurrence of paint flakes, which may strongly compromise the outcome of any source diagnostics efforts. [ABSTRACT FROM AUTHOR]

Highlights: [•] Two-point measurement approach enhanced by adoption of passive sampling techniques. [•] Benthic chamber stops assumption that chemical-concentration gradient is linear. [•] Passive sampling device increases flux-measurement accuracy and is a powerful tool. [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]

Passive sampling techniques have been widely used to determine the dissolved concentration profiles of hydrophobic organic compounds (HOCs) in sediment porewater. However, the effects of having a protection for the passive sampler on profiling HOCs concentrations in sediment porewater, especially in deep sediment, have remained unclear. To address this issue, low density polyethylene passive samplers with and without protectors, which consisted of glass fiber filter and porous stainless steel shield, were simultaneously deployed in sediment of the Dongjiang River, South China. The results showed that the protectors retarded the dissipation of performance reference compounds (PRCs) from the sampler by a factor of 2–9. The protectors seemed to exert a negligible effect on the measured concentrations of PAHs, BDE-47, and BDE-99 in surficial sediment porewater (0–14 cm depth) from both samplers. However, the sediment porewater concentration profiles of PAHs and BDE-47 from the sampler with protectors were in agreement with those normalized by dry weight in deep sediment (16–34 cm depth), indicating that a diffusion layer established by the protectors may minimize the probability of local depletion of the target analytes in deep sediment. In addition, the log K oc values of PAHs, BDE-47, and BDE-99 exhibited a slight increasing trend with sediment depth. This finding suggested that in situ passive sampling techniques could be a feasible tool in determining the site-specific log K oc values of HOCs at different sediment depths. Image 1 • Protectors significantly retarded the dissipation of PRCs. • Protectors did not affect the measured concentrations of PAHs in surficial porewater. • PAHs profile from the sampler with protectors was similar to that in deep sediment. [ABSTRACT FROM AUTHOR]