Ecotoxicological effects of silver nanoparticles in marine mussels.

As the production of silver nanoparticles (AgNPs) is becoming more prevalent, it is becoming increasingly necessary to understand the toxicological effects they can have on different ecosystems. In the marine bioindicator species M. galloprovincialis Lam we predicted toxicity and bioaccumulation of 5 nm alkane-coated and 50 nm uncoated silver nanoparticles (AgNPs) along with silver nitrate as a function of the actual dose level. We generated a time persistence model of silver in seawater and used the Area Under the Curve (AUC) as independent variable in the hazard assessment. This approach allowed us to evaluate unbiased ecotoxicological endpoints for acute (survival) and chronic toxicity (byssal adhesion). Logistic regression analysis rendered an overall LC5096h values of 0.81 ± 0.07 mg h L-1 irrespectively of the silver form. By contrast, for byssal adhesion regression analysis revealed a much higher toxicological potential of silver nitrate vs AgNPs with EC5024h values respectively of 0.0024 ± 0.0009 vs 0.053 ± 0.016 and 0.063 (no computable error for 50 nm AgNP) mg h L-1, undoubtedly confirming a prevalence of ionic silver effects over AgNPs. Bioaccumulation was more efficient for silver nitrate >5 nm AgNP >50 nm AgNP reflecting a parallel with the preferential uptake route / target organ. Finally, we derived Risk Quotient (RQs) for acute and chronic effects of nanosilver in shellfish and showed that the RQs are far from the Level of Concern (LoC) at current estimated environmental concentrations (EECs). This information can ultimately help researchers, policy makers, and industry professionals decide how to safely regulate and/or dispose of AgNPs.

The potential future contribution of shipping to acidification of the Baltic Sea.

International regulation of the emission of acidic sulphur and nitrogen oxides from commercial shipping has focused on the risks to human health, with little attention paid to the consequences for the marine environment. The introduction of stricter regulations in northern Europe has led to substantial investment in scrubbers that absorb the sulphur oxides in a counterflow of seawater. This paper examines the consequences of smokestack and scrubber release of acidic oxides in the Baltic Sea according to a range of scenarios for the coming decades. While shipping is projected to become a major source of strong acid deposition to the Baltic Sea by 2050, the long-term effect on the pH and alkalinity is projected to be significantly smaller than estimated from previous scoping studies. A significant contribution to this difference is the efficient export of surface water acidification to the North Sea on a timescale of 15-20 years.

Ecotoxicity testing and environmental risk assessment of iron nanomaterials for sub-surface remediation - Recommendations from the FP7 project NanoRem.

Nanoremediation with iron (Fe) nanomaterials opens new doors for treating contaminated soil and groundwater, but is also accompanied by new potential risks as large quantities of engineered nanomaterials are introduced into the environment. In this study, we have assessed the ecotoxicity of four engineered Fe nanomaterials, specifically, Nano-Goethite, Trap-Ox Fe-zeolites, Carbo-Iron® and FerMEG12, developed within the European FP7 project NanoRem for sub-surface remediation towards a test battery consisting of eight ecotoxicity tests on bacteria (V. fisheri, E. coli), algae (P. subcapitata, Chlamydomonas sp.), crustaceans (D. magna), worms (E. fetida, L. variegatus) and plants (R. sativus, L. multiflorum). The tested materials are commercially available and include Fe oxide and nanoscale zero valent iron (nZVI), but also hybrid products with Fe loaded into a matrix. All but one material, a ball milled nZVI (FerMEG12), showed no toxicity in the test battery when tested in concentrations up to 100 mg/L, which is the cutoff for hazard labeling in chemicals regulation in Europe. However it should be noted that Fe nanomaterials proved challenging to test adequately due to their turbidity, aggregation and sedimentation behavior in aqueous media. This paper provides a number of recommendations concerning future testing of Fe nanomaterials and discusses environmental risk assessment considerations related to these.

Effects of silver nanoparticles on the freshwater snail Physa acuta: The role of test media and snails' life cycle stage.

Silver nanoparticles (AgNPs) are widely used worldwide, most likely leading to their release into the environment and a subsequent increase of environmental concentrations. Studies of their deleterious effects on organisms is crucial to understand their environmental impacts. The freshwater snail Physa acuta was chosen to evaluate the potential deleterious effects of AgNPs and their counterpart AgNO3 , through water-only exposures. The toxicity of AgNPs is greatly influenced by medium composition. Thus, 2 media were tested: artificial pond water (APW) and modified APW (adapted by removing calcium chloride). Acute tests (96 h) were performed with juvenile and adult snails in both media to assess lethality, and egg mass chronic tests were conducted with APW medium only to assess embryo viability and mortality, carried out until 90% hatching success was reached in the control. Acute toxicity increased with decreasing shell length for both silver forms (ion and nanoparticle); that is, juveniles were more sensitive than adults. Different test media led to dissimilar median lethal concentrations, with chloride playing an important role in toxicity, most likely by complexation with silver ions, which would reduce the bioavailability, uptake, and toxicity of silver. Chronic tests showed that hatching success was more sensitive to silver in the ionic form than in the particulate form. Different forms of silver, exposure media, and life cycle stages led to different patterns of toxicity, highlighting an impairment in the snails' life cycle. Environ Toxicol Chem 2017;36:243-253. © 2016 SETAC.

Uptake and elimination kinetics of silver nanoparticles and silver nitrate by Raphidocelis subcapitata: The influence of silver behaviour in solution.

Raphidocelis subcapitata is a freshwater algae species that constitutes the basis of many aquatic trophic chains. In this study, R. subcapitata was used as a model species to investigate the kinetics of uptake and elimination of silver nanoparticles (AgNP) in comparison to silver nitrate (AgNO3) with particular focus on the Ag sized-fractions in solution. AgNP used in this study were provided in a suspension of 1 mg Ag/l, with an initial size of 3-8 nm and coated with an alkane material. Algae was exposed for 48 h to both AgNP and AgNO3 and sampled at different time points to determine their internal Ag concentration over time. Samples were collected and separated into different sized fractions: total (Agtot), water column Ag (Agwater), small particulate Ag (Agsmall.part.) and dissolved Ag (Agdis). At AgNO3 exposures algae reached higher bioconcentration factor (BCF) and lower elimination rate constants than at AgNP exposures, meaning that Ag is more readily taken up by algae in its dissolved form than in its small particulate form, however slowly eliminated. When modelling the kinetics based on the Agdis fraction, a higher BCF was found. This supports our hypothesis that Ag would be internalised by algae only in its dissolved form. In addition, algae images obtained by Coherent Anti-stokes Raman Scattering (CARS) microscopy demonstrated large aggregates of nanoparticles external to the algae cells with no evidence of its internalisation, thus providing a strong suggestion that these AgNP were not able to penetrate the cells and Ag accumulation happens through the uptake of Ag ions.

Silver nanoparticles and silver nitrate induce high toxicity to Pseudokirchneriella subcapitata, Daphnia magna and Danio rerio.

Silver nanoparticles (AgNP) have gained attention over the years due to the antimicrobial function of silver, which has been exploited industrially to produce consumer goods that vary in type and application. Undoubtedly the increase of production and consumption of these silver-containing products will lead to the entry of silver compounds into the environment. In this study we have used Pseudokirchneriella subcapitata, Daphnia magna and Danio rerio as model organisms to investigate the toxicity of AgNP and AgNO3 by assessing different biological endpoints and exposure periods. Organisms were exposed following specific and standardized protocols for each species/endpoints, with modifications when necessary. AgNP were characterized in each test-media by Transmission Electron Microscopy (TEM) and experiments were performed by Dynamic Light Scattering (DLS) to investigate the aggregation and agglomeration behavior of AgNP under different media chemical composition and test-period. TEM images of AgNP in the different test-media showed dissimilar patterns of agglomeration, with some agglomerates inside an organic layer, some loosely associated particles and also the presence of some individual particles. The toxicity of both AgNO3 and AgNP differ significantly based on the test species: we found no differences in toxicity for algae, a small difference for zebrafish and a major difference in toxicity for Daphnia magna.

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(-1), 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.

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(CIT)) and polyvinylpyrrolidone (AgNP(PVP)) coated manufactured silver nanoparticles, as well as AgNO(3) (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 10 mg L(-1) 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 0.1 mg L(-1) to 10 mg L(-1). Results show that AgNP(CIT) nanoparticles are readily taken up into gill cell monolayers while uptake was less for AgNP(PVP). In contrast, it appears that the slightly smaller AgNP(PVP) were transported through cultured multilayers to a higher extent, with transport rates generally being in the ng cm(-2) range for 48 h 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.