Limited Effectiveness of Carbonaceous Sorbents in Sequestering Aged Organic Contaminants in Sediments.

Carbonaceous materials are often proposed for use in restoring soils or sediments contaminated with hydrophobic organic contaminants (HOCs). However, the contamination of most sites is a result of historical events, where HOCs have resided in the solid compartment for many years or decades. The prolonged contact time, or aging, leads to reduced contaminant availability and likely diminished effectiveness of using sorbents. In this study, three different carbonaceous sorbents, i.e., biochars, powdered activated carbon, and granular activated carbon, were amended to a Superfund site marine sediment contaminated with DDT residues from decades ago. The amended sediments were incubated in seawater for up to 1 year, and the freely dissolved concentration (Cfree) and the biota-sediment accumulation factors (BSAFs) for a native polychaete (Neanthes arenaceodentata) were measured. Even though the bulk sediment concentrations were very high (6.4-154.9 µg/g OC), both Cfree and BSAFs were very small, ranging from nd to 1.34 ng/L and from nd to 0.024, respectively. The addition of carbonaceous sorbents, even at 2% (w/w), did not consistently lead to reduced DDT bioaccumulation. The limited effectiveness of carbonaceous sorbents was attributed to the low DDT availability due to prolonged aging, highlighting the need for considering contaminant aging when using sorbents for remediation.

Occurrence and Probable Sources of Urban-Use Insecticides in Marine Sediments off the Coast of Los Angeles.

Insecticides such as pyrethroids and fipronil are used in large amounts in both agricultural and urban settings and have the potential to elicit toxicity to nontarget aquatic organisms. In California, like in many other regions of the world, urban centers are located along the coast, and it is documented that urban-use insecticides enter the marine environment, where little is known about their occurrence and consequences. In this study, we measured the spatial distribution of pyrethroids and fipronil (and its metabolites) on the Palos Verdes Shelf off the coast of Los Angeles. Total pyrethroid levels ranged from nd to 170 µg/kg (dry weight), and fipronil sulfide levels ranged from 1.8 to 5.6 µg/kg. Two pyrethroids were traced to wastewater effluent discharge, while two others and fipronil sulfide were traced to to surface runoff. Toxicity units (TUs) were estimated for benthic invertebrates, which ranged from no toxicity (nt) to 146 for total pyrethroids, and 0.09 to 1.6 and 4.2 to 75 for fipronil sulfide, depending on the indicator species. Therefore, near-shore deposition of urban-use insecticides due to wastewater discharge and surface runoff poses a significant risk to marine benthic invertebrates and highlights the importance of monitoring near-shore ocean environments and developing mitigation strategies to reduce seaward movement.

Inference of Organophosphate Ester Emission History from Marine Sediment Cores Impacted by Wastewater Effluents.

Organophosphate esters (OPEs) have been in use as flame retardants for many decades, with their actual usage varying over time. Knowledge of the emission history of OPEs is valuable for improving our prediction of their environmental loadings and associated risks. In this study, concentrations and compositions of 10 OPEs were measured in three dated sediment cores from the Palos Verdes Shelf (PVS) off the coast of Los Angeles, which has been impacted by wastewater treatment plant (WWTP) effluents for over a century. The total OPE concentrations varied from 0.68 to 1064 ng/g along the sediment profile, with two apparent peaks. The first peak occurred in the 1970s, coinciding with peak emissions from WWTPs. The second peak appeared in the 2000s and was possibly attributed to increased consumption of OPEs as replacement flame retardants. Since downward movement of OPEs in the PVS sediment bed was retarded by their slow desorption, the reconstructed history likely provided an accurate picture of OPE emissions in Southern California and North America. These findings suggest that the near-shore marine sediments affected by WWTP effluents could serve as an environmental proxy documenting history in OPE use and emissions.

Effect of aging on bioaccessibility of DDTs and PCBs in marine sediment.

Hydrophobic legacy contaminants like dichlorodiphenyltrichloroethane (DDT) and polychlorinated biphenyls (PCBs) were banned almost half a century ago. While their residues still remain in many environmental compartments, they have undergone extensive aging and likely have lower bioaccessibility (the available fraction) compared to fresh residues. However, risk assessment relies heavily on the use of total chemical concentration, rather than accounting for age-diminished bioaccessibility, likely leading to overestimated risks. In this study, we used 24 h Tenax desorption to measure the potential bioaccessibility of DDTs and PCBs in two sediment cores taken from the Palos Verdes Shelf Superfund site in the Pacific Ocean. The total concentrations of DDTs and PCBs from the core located at the sewage outfall (8C) were as high as 41,000-15,700 µg/kg (dry weight, dw) and 530-2600 µg/kg dw, respectively, while those from a location 7 km northeast of the outfall (3C) were 2-3 orders of magnitude lower. Bioaccessibility estimated by 24-h Tenax-aided desorption (F24h) decreased in the order of DDD > DDE > DDT for DDT derivatives, and PCB 52 > PCB 70 > PCB 153 for PCB congeners, showing a negative correlation with their log Kow. Due to the extensive aging, F24h values were <20% of the total chemical concentration for most contaminants and <5% for DDT, DDE and PCB 153, suggesting that aging greatly diminished their bioavailability. However, a quantitative relationship between F24h and sediment age along the vertical profile was not found, likely because the contaminant residues had undergone aging before their offsite transport and deposition onto the ocean floor. As the use of man-made chemicals such as DDT and PCBs was discontinued in the U.S. many decades ago, the reduction in their bioavailability due to aging may be universal and should be taken into consideration to avoid overly conservative risk predictions or unnecessary mitigation interventions.

Development of polyurethane-based passive samplers for ambient monitoring of urban-use insecticides in water.

Widespread use of insecticides for the control of urban pests such as ants, termites, and spiders has resulted in contamination and toxicity in urban aquatic ecosystems in different regions of the world. Passive samplers are a convenient and integrative tool for in situ monitoring of trace contaminants in surface water. However, the performance of a passive sampler depends closely on its affinity for the target analytes, making passive samplers highly specific to the types of contaminants being monitored. The goal of this study was to develop a passive sampler compatible with a wide range of insecticides, including the strongly hydrophobic pyrethroids and the weakly hydrophobic fipronil and organophosphates. Of six candidate polymeric thin films, polyurethane film (PU) was identified to be the best at enriching the test compounds. The inclusion of stable isotope labeled analogs as performance reference compounds (PRCs) further allowed the use of PU film for pyrethroids under non-equilibrium conditions. The PU sampler was tested in a large aquarium with circulatory water flow, and also deployed at multiple sites in surface streams in southern California. The concentrations of pesticides derived from the PU sampler ranged from 0.5 to 18.5 ng/L, which were generally lower than the total chemical concentration measured by grab samples, suggesting that suspended particles and dissolved organic matter in water rendered them less available. The influence of suspended particles and dissolved organic matter on bioavailability was more pronounced for pyrethroids than for fipronils. The results show that the developed PU film sampler, when coupled with PRCs, may be used for rapid and sensitive in-situ monitoring of a wide range of insecticides in surface water.

Historical record and fluxes of DDTs at the Palos Verdes Shelf Superfund site, California.

Marine sediments at many locations in the world are contaminated with a wide range of persistent organic pollutants. The Palos Verdes Shelf (PVS) is located in the ocean off the coast of Los Angeles, California and has been listed as a Superfund site by the US EPA since 1997, because of heavy contamination of DDTs and PCBs. However, little is known about the historical trend in the deposition of DDTs as a result of decades-long discharge of wastewater effluents. In this study, sediment cores were taken from the PVS site and determined for DDT and its metabolites including DDE and DDD (denoted as DDTs). Individual DDTs were found in the majority (95%) of the samples analyzed. The highest ∑DDT concentrations were found in three cores along the 60-meter isobath with geometric means of 31300, 7490, and 5010ng/gdw and medians of 82400, 17300, and 5200ng/g dw, respectively. Among DDT congeners, p,p'-DDE, o,p'-DDE and p,p'-DDD were predominant, contributing to approximately 54%, 27%, and 14% of the ΣDDTs in sediment. The vertical profiles of concentrations of contaminants in the sediment cores were examined. For most of the cores, a steady increase in the concentrations of DDTs during 1940s to 1980s was observed, while the concentrations declined gradually toward the surficial layers. On the basis of the mass flux of DDTs calculated and the area of the PVS Superfund site, we estimated the total deposition amount of DDTs in sediment and the deposition amount of ΣDDTs in this region during 1947-1971 was 132 tons, which was fairly close to what was reported in earlier studies for industrial wastewater discharge in the PVS site (870-1450tons). Our findings suggest that the elevated levels of DDTs in sediment from the PVS site are linked to the discharge of these contaminants between the 1940s-1980s.