We report results on the first field-scale application of activated carbon (AC) amendment to contaminated sediment for in-situ stabilization of polychlorinated biphenyls (PCBs). The test was performed on a tidal mud flat at South Basin, adjacent to the former Hunters Point Naval Shipyard, San Francisco Bay, CA. The major goals of the field study were to (1) assess scale up of the AC mixing technology using two available, large-scale devices, (2) validate the effectiveness of the AC amendment at the field scale, and (3) identify possible adverse effects of the remediation technology. Also, the test allowed comparison among monitoring tools, evaluation of longer-term effectiveness of AC amendment, and identification of field-related factors that confound the performance of in-situ biological assessments. Following background pretreatment measurements, we successfully incorporated AC into sediment to a nominal 30 cm depth during a single mixing event, as confirmed by total organic carbon and black carbon contents in the designated test plots. The measured AC dose averaged 2.0-3.2 wt% and varied depending on sampling locations and mixing equipment. AC amendment did not impact sediment resuspension or PCB release into the water column over the treatment plots, nor adversely impactthe existing macro benthic community composition, richness, or diversity. The PCB bioaccumulation in marine clams was reduced when exposed to sediment treated with 2% AC in comparison to the control plot Field-deployed semi permeable membrane devices and polyethylene devices showed about 50% reduction in PCB uptake in AC-treated sediment and similar reduction in estimated pore-water PCB concentration. This reduction was evident even after 13-month post-treatment with then 7 months of continuous exposure, indicating AC treatment efficacy was retained for an extended period. Aqueous equilibrium PCB concentrations and PCB desorption showed an AC-dose response. Field-exposed AC after 18 months retained a strong stabilization capability to reduce aqueous equilibrium PCB concentrations by about 90%, which also supports the long-term effectiveness of AC in the field. Additional mixing during or after AC deployment, increasing AC dose, reducing AC-particle size, and sequential deployment of AC dose will likely improve AC-sediment contact and overall effectiveness. The reductions in PCB availability observed with slow mass transfer under field conditions calls for predictive models to assess the long-term trends in pore-water PCB concentrations and the benefits of alternative in-situ AC application and mixing strategies.

This review paper reports the consensus of a technical workshop hosted by the European network, NanoImpactNet (NIN). The workshop aimed to review the collective experience of working at the bench with manufactured nanomaterials (MNMs), and to recommend modifications to existing experimental methods and OECD protocols. Current procedures for cleaning glassware are appropriate for most MNMs, although interference with electrodes may occur. Maintaining exposure is more difficult with MNMs compared to conventional chemicals. A metal salt control is recommended for experiments with metallic MNMs that may release free metal ions. Dispersing agents should be avoided, but if they must be used, then natural or synthetic dispersing agents are possible, and dispersion controls essential. Time constraints and technology gaps indicate that full characterisation of test media during ecotoxicity tests is currently not practical. Details of electron microscopy, dark-field microscopy, a range of spectroscopic methods (EDX, XRD, XANES, EXAFS), light scattering techniques (DLS, SLS) and chromatography are discussed. The development of user-friendly software to predict particle behaviour in test media according to DLVO theory is in progress, and simple optical methods are available to estimate the settling behaviour of suspensions during experiments. However, for soil matrices such simple approaches may not be applicable. Alternatively, a Critical Body Residue approach may be taken in which body concentrations in organisms are related to effects, and toxicity thresholds derived. For microbial assays, the cell wall is a formidable barrier to MNMs and end points that rely on the test substance penetrating the cell may be insensitive. Instead assays based on the cell envelope should be developed for MNMs. In algal growth tests, the abiotic factors that promote particle aggregation in the media (e.g. ionic strength) are also important in providing nutrients, and manipulation of the media to control the dispersion may also inhibit growth. Controls to quantify shading effects, and precise details of lighting regimes, shaking or mixing should be reported in algal tests. Photosynthesis may be more sensitive than traditional growth end points for algae and plants. Tests with invertebrates should consider non-chemical toxicity from particle adherence to the organisms. The use of semi-static exposure methods with fish can reduce the logistical issues of waste water disposal and facilitate aspects of animal husbandry relevant to MMNs. There are concerns that the existing bioaccumulation tests are conceptually flawed for MNMs and that new test(s) are required. In vitro testing strategies, as exemplified by genotoxicity assays, can be modified for MNMs, but the risk of false negatives in some assays is highlighted. In conclusion, most protocols will require some modifications and recommendations are made to aid the researcher at the bench.

Carbon nanotubes (NTs) may be among the most useful engineered nanomaterials for structural applications but could be difficult to study in ecotoxicological evaluations using existing tools relative to nanomaterials with a lower aspect ratio. Whereas the hydrophobicity and van der Waals interactions of NTs may suggest aggregation and sedimentation in aquatic systems, consideration regarding how engineered surface modifications influence their environmental fate and toxicology is needed. Surface modifications (e.g., functional groups and coatings) are intended to create conditions to make NTs dispersible in aqueous suspension, as required for some applications. In the present study, column stability and settling experiments indicated that raw, multiwalled NTs (MWNTs) settled more rapidly than carbon black and activated carbon particles, suggesting sediment as the ultimate repository. The presence of functional groups, however, slowed the settling of MWNTs (increasing order of stability: hydroxyl > carboxyl > raw), especially in combination with natural organic matter (NOM). Stabilized MWNTs in high concentrations of NOM provided relevance for water transport and toxicity studies. Aqueous exposures to raw MWNTs decreased Ceriodaphnia dubia viability, but such effects were not observed during exposure to functionalized MWNTs (> 80 mg/L). Sediment exposures of the amphipods Leptocheirus plumulosus and Hyalella azteca to different sizes of sediment-borne carbon particles at high concentration indicated mortality increased as particle size decreased, although raw MWNTs induced lower mortality (median lethal concentration [LC50], 50 to >264 g/kg) than carbon black (LC50, 18-40 g/kg) and activated carbon (LC50, 12-29 g/kg). Our findings stress that it may be inappropriate to classify all NTs into one category in terms of their environmental regulation.