Nanomaterial Fate in Seawater: A Rapid Sink or Intermittent Stabilization?

Coastal seas and oceans receive engineered nanoparticles that are released from nano-enabled consumer and industrial products and incidental nanoparticles that are formed as byproducts of combustion and friction. The marine environment is often perceived as a rapid sink for particles, because of the high salinity promoting the attachment between particles producing heavy agglomerates that sediment on the seafloor. In this work the effect of seasonal production of extracellular polymeric substances (EPS) on particle stability is tested using seawater collected from the Gullmarn fjord in the winter, spring, and summer. A novel approach is used that is based on light scattering of the bulk particle population for tracking agglomerates and of single particles for tracking particles smaller than approximately 300 nm. Results show that organic particles formed from EPS during algal blooms are capable of stabilizing nanoparticles in marine waters for at least 48 h. In contrast, particles agglomerate rapidly in the same seawater that has previously been filtered through 0.02 mu m pore size membranes. Furthermore, particles with fibrillar shape have been detected using atomic force microscopy, supporting the argument that organic particles from EPS are responsible for the stabilization effect. These results suggest that seasonal biological activity can act as an intermittent stabilization factor for nanoparticles in marine waters

Asymmetrical flow field flow fractionation - Multidetection system as a tool for studying metal-alginate interactions

The present study explores the potential use of asymmetrical flow field flow fractionation (aFlFFF) with a multidetection system for the study of metal-alginate interactions. aFlFFF, coupled on-line to a differential refractive index and seven angle laser light scattering detectors was used to provide information on the alginate size distributions. In parallel, the metal distributions of metal-alginate complexes were probed by aFlFFF-high resolution inductively coupled plasma-mass spectrometry. Average values and continuous distributions of molar masses, radiuses of gyration and hydrodynamic radiuses, which are critical for understanding the role of alginates as carriers of metal pollutants, were evaluated in presence of Pb or Cd and compared with those in metal-free solutions of alginate. The values of number average and weight average molar mass, weight average radius of gyration and shape factor for alginate were 150 and 188 kg mol(-1), 53 nm and 1.7, respectively. Alginate molar mass and radius of gyration distributions were slightly shifted to higher values by the addition of micromolar concentrations of Pb or Cd. The alginate size distribution in the presence of Cd was similar to the alginate-alone control, whereas in the presence of Pb the size distribution was broader with a shift of the maximum toward higher molar masses

Application of cross-flow ultrafiltration for the determination of colloidal abundances in suboxic ferrous-rich ground waters

A suboxic groundwater from a sandy coastal aquifer was sampled using a new air free, large volume sampling method. Subsequent processing for size fractionation was completed with a modified cross-flow ultrafiltration (CFF) system equipped with a 1 kDa CFF membrane. By purging the CFF system with nitrogen, no oxygen was able to reach the sample. With this optimization, the sample was processed with higher than 90% recovery in terms of both iron and phosphate. Only about 4% of iron and 20% of phosphate in the filtered (0.2 mu m) groundwater sample was found to be in colloidal form in the groundwater. In contrast, if no care was taken to maintain the suboxic environment of the original sample, iron was rapidly and completely oxidized and subsequently adsorbed to the CFF membrane. Other elements, such as phosphorus, were also lost to the CFF membrane to a substantial degree, and the mechanism is most likely coprecipitation with iron oxides. This study thus strongly supports the importance of maintaining ambient redox conditions during sampling and fractionation, especially for the determinations of colloid abundances in groundwater. (c) 2006 Elsevier B.V. All rights reserved

Uptake and effects of manufactured silver nanoparticles in rainbow trout (Oncorhynchus mykiss) gill cells

Nanoparticles are already widely used in technology, medicine and consumer products, but there are limited data on their effects on the aquatic environment. In this study the uptake and effect of citrate (AgNP) and polyvinylpyrrolidone (AgNP) coated manufactured silver nanoparticles, as well as AgNO (Ag) were tested using primary gill cells of rainbow trout (Oncorhynchus mykiss). Prior to use, the nanoparticles were characterized for size, surface charge and aggregation behavior. Gill cells were cultured either as monolayers on solid support, or as multilayers on a permeable support cell culturing system, enabling transport studies. The uptake of silver nanoparticles and Ag after exposure to 10mgL was determined with microscopical methods and inductively coupled plasma mass spectrometry (ICP-MS). Cytotoxicity, in terms of membrane integrity, as well as oxidative stress (depletion of reduced glutathione) was tested at silver concentrations ranging from 0.1mgL to 10mgL. Results show that AgNP nanoparticles are readily taken up into gill cell monolayers while uptake was less for AgNP. In contrast, it appears that the slightly smaller AgNP were transported through cultured multilayers to a higher extent, with transport rates generally being in the ngcm range for 48h exposures. Transport rates for all exposures were dependent on the epithelial tightness. Moderate cytotoxic effects were seen for all silver treatments. Levels of reduced glutathione were elevated in contrast to control groups, pointing on a possible overcompensation reaction. Taken together silver nanoparticles were taken up into cells and did cause silver transport over cultured epithelial layers with uptake and transport rates being different for the two nanoparticle species. All silver treatments had measurable effects on cell viability

The role of nanominerals and mineral nanoparticles in the transport of toxic trace metals: Field-flow fractionation and analytical TEM analyses after nanoparticle isolation and density separation

Nanominerals and mineral nanoparticles from a mining-contaminated river system were examined to determine their potential to co-transport toxic trace metals. A recent large-scale dam removal project on the Clark Fork River in western Montana (USA) has released reservoir and upstream sediments contaminated with toxic trace metals (Pb, As, Cu and Zn), which had accumulated there as a consequence of more than a century and a half of mining activity proximal to the river's headwaters near the cities of Butte and Anaconda. To isolate the high-density nanoparticle fractions from riverbed and bank sediments, a density separation with sodium polytungstate (2.8 g/cm(3)) was employed prior to a standard nanoparticle extraction procedure. The stable, dispersed nanoparticulate fraction was then analyzed by analytical transmission electron microscopy (aTEM) and flow field-flow fractionation (FlFFF) coupled to both multi-angle laser light scattering (MALLS) and high-resolution, inductively coupled plasma mass spectrometry (HR-ICPMS). FlFFF analysis revealed a size distribution in the nano range and that the elution profiles of the trace metals matched most closely to that for Fe and Ti. aTEM confirmed these results as the majority of the Fe and Ti oxides analyzed were associated with one or more of the trace metals of interest. The main mineral phases hosting trace metals are goethite, ferrihydrite and brookite. This demonstrates that they are likely playing a significant role in dictating the transport and distribution of trace metals in this river system, which could affect the bioavailability and toxicity of these metals. (C) 2012 Elsevier Ltd. All rights reserved

Effects of silver and gold nanoparticles on rainbow trout (Oncorhynchus mykiss) hepatocytes

The use of nanomaterials is rapidly increasing, while little is known about their possible ecotoxicological effects. This work investigates the toxic effects of silver (Ag) and gold (Au) nanoparticles on rainbow trout hepatocytes. In addition to toxicity assessment the particles were characterized by transmission electron microscopy (TEM) and nanoparticle tracking analysis (NTA). Hepatocyte primary cultures were exposed to Au and Ag nanoparticles, with and without dissolved organic carbon (DOC), as well as HAuCl and AgNO as ionic solutions at concentrations up to 17.4 mg/L and 19 mg/L, respectively. Ag and Au particles were within the small nanometer size range when dispersed in pure water. In media with higher ionic strength and DOC, particles tended to agglomerate. Cytotoxicity assessments showed that Ag nanoparticles caused a significant reduction in membrane integrity and cellular metabolic activity in a concentration-dependent manner. Au nanoparticles caused a threefold elevation of ROS levels, but no cytotoxicity occurred at concentrations tested. The addition of DOC did not alter the particles potency of cytotoxicity or ROS induction capacity. The current study shows that Ag and Au nanoparticles have adverse effects on rainbow trout hepatocytes at low mg/L concentrations

Marine plastic litter on Small Island Developing States (SIDS) : Impacts and measures

Plastic waste that ends up in the oceans as marine litter is a tangible and urgent environmental pressure reaching even the most remote parts of the global oceans. It impacts marine life from plankton to whales and turtles to albatrosses. Public awareness on how the modern lifestyle and the use of plastics in all sectors of society has influenced the marine ecosystems in the lastdecades is growing, and an emerging discourse about countermeasures of all types can be seen in policies enacted by authorities in national, regional, and international policy arenas. Different coastal areas have launched Regional Action Plans (RAP) on marine litter that provide structured measures that need to be taken and general advice adapted to the respective region.However, the scale of the problem is not only global in dimension, it also cuts across all sectors in society, and until the use of materials in society becomes sustainable, plastic waste will continues to flow into the seas. This report focuses on how marine plastic litter affects Small Island Developing States (SIDS) because these are considered to be more directly vulnerable to environmental changes, including marine litter, than other countries

Characterization of the effluent from a nanosilver producing washing machine

The increasing number of nanomaterial based consumer products raises concerns about their possible impact on the environment. This study provides an assessment of the effluent from a commercially available silver nanowashing machine. The washing machine released silver in its effluent at an average concentration of 11μgL, as determined by inductive coupled mass spectrometry (ICP-MS). The presence of silver nanoparticles (AgNPs) was confirmed by single particle ICP-MS as well as ion selective electrode measurements and filtration techniques. Size measurements showed particles to be in the defined nanosize range, with an average size of 10nm measured with transmission electron microscopy (TEM) and 60-100nm determined with nanoparticle tracking analysis (NTA). The effluent was shown to have negative effects on a natural bacterial community as its abundance was clearly reduced when exposed to the nanowash water. If washing machines capable of producing AgNPs become a common feature of households in the future, wastewater will contain significant loadings of AgNPs which might be released into the environment

Nanomaterials for environmental studies: Classification, reference material issues, and strategies for physico-chemical characterisation

NanoImpactNet is a European Commission Framework Programme 7 (FP7) funded project that provides a forum for the discussion of current opinions on nanomaterials in relation to human and environmental issues. In September 2008, in Zurich, a NanoImpactNet environmental workshop focused on three key questions: 1. What properties should be characterised for nanomaterials used in environmental and ecotoxicology studies? 2. What reference materials should be developed for use in environmental and ecotoxicological studies? 3. Is it possible to group different nanomaterials into categories for consideration in environmental studies? Such questions have been, at least partially, addressed by other projects/workshops especially in relation to human health effects. Such projects provide a useful basis on which this workshop was based, but in this particular case these questions were reformulated in order to focus specifically on environmental studies. The workshop participants, through a series of discussion and reflection sessions, generated the conclusions listed below. The physicochemical characterisation information identified as important for environmental studies included measures of aggregation/agglomeration/dispersability, size, dissolution (solubility), surface area, surface charge, surface chemistry/composition, with the assumption that chemical composition would already be known. There is a need to have test materials for ecotoxicology, and several substances are potentially useful, including TiO2 nanoparticles, polystyrene beads labelled with fluorescent dyes, and silver nanoparticles. Some of these test materials could then be developed into certified reference materials over time. No clear consensus was reached regarding the classification of nanomaterials into categories to aid environmental studies, except that a chemistry-based classification system was a reasonable starting point, with some modifications. It was suggested, that additional work may be required to derive criteria that can be used to generate such categories, that would also include aspects of the material structure and physical behaviour