Anders Baun

Present and Long-Term Composition of MSW Landfill Leachate: A Review

The major potential environmental impacts related to landfill leachate are pollution of groundwater and surface waters. Landfill leachate contains pollutants that can be categorized into four groups (dissolved organic matter, inorganic macrocomponents, heavy metals, and xenobiotic organic compounds). Existing data show high leachate concentrations of all components in the early acid phase due to strong decomposition and leaching. In the long methanogenic phase a more stable leachate, with lower concentrations and a low BOD/COD-ratio, is observed. Generally, very low concentrations of heavy metals are observed. In contrast, the concentration of ammonia does not decrease, and often constitutes a major long-term pollutant in leachate. A broad range of xenobiotic organic compounds is observed in landfill leachate. The long-term behavior of landfills with respect to changes in oxidation-reduction status is discussed based on theory and model simulations. It seems that the somewhere postulated enhanced release of accumulated heavy metals would not take place within the time frames of thousands of years. This is supported by a few laboratory investigations. The existing data and model evaluations indicate that the xenobiotic organic compounds in most cases do not constitute a major long-term problem. This may suggest that ammonia will be of most concern in the long run.

Environmental behavior and ecotoxicity of engineered nanoparticles to algae, plants, and fungi

Developments in nanotechnology are leading to a rapid proliferation of new materials that are likely to become a source of engineered nanoparticles (ENPs) to the environment, where their possible ecotoxicological impacts remain unknown. The surface properties of ENPs are of essential importance for their aggregation behavior, and thus for their mobility in aquatic and terrestrial systems and for their interactions with algae, plants and, fungi. Interactions of ENPs with natural organic matter have to be considered as well, as those will alter the ENPs aggregation behavior in surface waters or in soils. Cells of plants, algae, and fungi possess cell walls that constitute a primary site for interaction and a barrier for the entrance of ENPs. Mechanisms allowing ENPs to pass through cell walls and membranes are as yet poorly understood. Inside cells, ENPs might directly provoke alterations of membranes and other cell structures and molecules, as well as protective mechanisms. Indirect effects of ENPs depend on their chemical and physical properties and may include physical restraints (clogging effects), solubilization of toxic ENP compounds, or production of reactive oxygen species. Many questions regarding the bioavailability of ENPs, their uptake by algae, plants, and fungi and the toxicity mechanisms remain to be elucidated.

Mixtures of Chemical Pollutants at European Legislation Safety Concentrations: How Safe Are They?

The risk posed by complex chemical mixtures in the environment to wildlife and humans is increasingly debated, but has been rarely tested under environmentally relevant scenarios. To address this issue, two mixtures of 14 or 19 substances of concern (pesticides, pharmaceuticals, heavy metals, polyaromatic hydrocarbons, a surfactant, and a plasticizer), each present at its safety limit concentration imposed by the European legislation, were prepared and tested for their toxic effects. The effects of the mixtures were assessed in 35 bioassays, based on 11 organisms representing different trophic levels. A consortium of 16 laboratories was involved in performing the bioassays. The mixtures elicited quantifiable toxic effects on some of the test systems employed, including i) changes in marine microbial composition, ii) microalgae toxicity, iii) immobilization in the crustacean Daphnia magna, iv) fish embryo toxicity, v) impaired frog embryo development, and vi) increased expression on oxidative stress-linked reporter genes. Estrogenic activity close to regulatory safety limit concentrations was uncovered by receptor-binding assays. The results highlight the need of precautionary actions on the assessment of chemical mixtures even in cases where individual toxicants are present at seemingly harmless concentrations.

Toxicity and bioaccumulation of xenobiotic organic compounds in the presence of aqueous suspensions of aggregates of nano-C60

The potential of C(60)-nanoparticles (Buckminster fullerenes) as contaminant carriers in aqueous systems was studied in a series of toxicity tests with algae (Pseudokirchneriella subcapitata) and crustaceans (Daphnia magna). Four common environmental contaminants (atrazine, methyl parathion, pentachlorophenol (PCP), and phenanthrene) were used as model compounds, representing different physico-chemical properties and toxic modes of action. The aggregates of nano-C(60) formed over 2 months of stirring in water were mixed with model compounds 5 days prior to testing. Uptake and excretion of phenanthrene in 4-days-old D. magna was studied with and without addition of C(60) in aqueous suspensions. It was found that 85% of the added phenanthrene sorbed to C(60)-aggregates >200 nm whereas about 10% sorption was found for atrazine, methyl parathion, and pentachlorophenol. In algal tests, the presence of C(60)-aggregates increased the toxicity of phenanthrene with 60% and decreased toxicity of PCP about 1.9 times. Addition of C(60)-aggregates reduced the toxicity of PCP with 25% in tests with D. magna, whereas a more than 10 times increase in toxicity was observed for phenanthrene when results were expressed as water phase concentrations. Thus, results from both toxicity tests show that phenanthrene sorbed to C(60)-aggregates is available for the organisms. For atrazine and methyl parathion no statistically significant differences in toxicities could be observed in algal and daphnid tests as a result of the presence of C(60)-aggregates. In bioaccumulation studies with phenanthrene in D. magna it was found that the uptake of phenanthrene was faster when C(60) was present in suspension and that a 1.7 times higher steady-state concentration was reached in the animals. However, a very fast clearance took place when animals were transferred to clean water resulting in no accumulation of phenanthrene. This study is the first to demonstrate the influence of C(60)-aggregates on aquatic toxicity and bioaccumulation of other environmentally relevant contaminants. The data provided underline that not only the inherent toxicity of manufactured nanoparticles, but also interactions with other compounds and characterisation of nanoparticles in aqueous suspension are of importance for risk assessment of nanomaterials.

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 TiO(2) 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.

Algal testing of titanium dioxide nanoparticles—Testing considerations, inhibitory effects and modification of cadmium bioavailability

The ecotoxicity of three different sizes of titanium dioxide (TiO(2)) particles (primary particles sizes: 10, 30, and 300nm) to the freshwater green alga Pseudokirchneriella subcapitata was investigated in this study. Algal growth inhibition was found for all three particle types, but the physiological mode of action is not yet clear. It was possible to establish a concentration/dose-response relationship for the three particle sizes. Reproducibility, however, was affected by concentration-dependent aggregation of the nanoparticles, subsequent sedimentation, and possible attachment to vessel surfaces. It is also believed that heteroaggregation, driven by algal exopolymeric exudates, is occurring and could influence the concentration-response relationship. The ecotoxicity of cadmium to algae was investigated both in the presence and absence of 2mg/L TiO(2). The presence of TiO(2) in algal tests reduced the observed toxicity due to decreased bioavailability of cadmium resulting from sorption/complexation of Cd(2+) ions to the TiO(2) surface. However, for the 30nm TiO(2) nanoparticles, the observed growth inhibition was greater than what could be explained by the concentration of dissolved Cd(II) species, indicating a possible carrier effect, or combined toxic effect of TiO(2) nanoparticles and cadmium. These results emphasize the importance of systematic studies of nanoecotoxicological effects of different sizes of nanoparticles and underline the fact that, in addition to particle toxicity, potential interactions with existing environmental contaminants are also of crucial importance in assessing the potential environmental risks of nanoparticles.

Categorization framework to aid hazard identification of nanomaterials

The physical, chemical and biological properties of various nanomaterials differ substantially – as do the potential risks they pose. We argue that nanomaterials must be categorized based on the location of the nanoscale structure in the system/material before their hazards can be assessed and propose a categorization framework that enables scientists and regulators to identify the categories of nanomaterials systematically. The framework is applied to a suggested hazard identification approach aimed at identifying causality between inherent physical and chemical properties and observed adverse effects reported in the literature. We tested the workability of the proposed procedure using nanoparticles as an illustrative case study. A database was generated noting the reported inherent physical and chemical properties of the nanoparticles tested and the main effects observed. 428 studies were noted in the database reporting on a total of 965 nanoparticles. We found that although a limited number of studies have been reported on ecotoxicity, more than 120 and 270 have been reported on mammalian toxicity and cytotoxicity, respectively. In general there was a lack of characterization of the nanoparticles studied and it was not possible to link specific properties of nanoparticles to the observed effects. Our study shows that future research strategies must have a strong focus on characterization of the nanoparticles tested.

Ecotoxicity of mixtures of antibiotics used in aquacultures

More or less well-defined mixtures of antibiotics used in aquacultures may be distributed in the aquatic environment. Therefore, a systematic mixture ecotoxicity study was performed with the aquaculture antibiotics oxytetracycline, oxolinic acid, erythromycin, florfenicol, and flumequine. Test organisms were freshwater algae (Pseudokirchneriella subcapitata), activated sludge microorganisms, and luminescent bacteria (Vibrio fischeri). Design and statistical analysis of test results were based on isobolographic analysis. Synergistic effects were observed when combinations of erythromycin and oxytetracycline were tested on activated sludge microorganisms, and in these cases model predictions indicate independent action on the different bacterial species in the sludge. As predicted from the modes of action, concentration addition was evident when flumequine and oxolinic acid were mixed and tested on sludge bacteria. In the algae test, the combined toxicity of antibiotics could not be predicted based on knowledge of the modes of action of the individual compounds. Independent of the test species, our results gave examples of combined effects that were higher than predicted based on the assumption of concentration addition. This result underlines the need to consider the effects of mixtures of antibiotics on environmental organisms. The isobolographic method appears to be a suitable tool for this purpose, particularly for well-defined mixtures with few substances.

Late lessons from early warnings for nanotechnology

A new technology will only be successful if those promoting it can show that it is safe, but history is littered with examples of promising technologies that never fulfilled their true potential and/or caused untold damage because early warnings about safety problems were ignored. The nanotechnology community stands to benefit by learning lessons from this history.

How to assess exposure of aquatic organisms to manufactured nanoparticles

Ecological risk of chemicals is measured by the quotient of predicted no-effect concentrations and predicted exposure concentrations, which are hard to assess for manufactured nanomaterials (NMs). This paper proposes modifications to currently used models, in order to make them suitable for estimating exposure concentrations of NMs in the aquatic environment. We have evaluated the adequacy of the current guidance documents for use with NMs and conclude that nano-specific fate processes, such as sedimentation and dissolution need to be incorporated. We have reviewed the literature on sedimentation and dissolution of NMs in environmentally relevant systems. We deduce that the overall kinetics of water-sediment transport of NMs should be close to first order. The lack of data on dissolution of NMs under environmentally realistic conditions calls for a pragmatic decision on which rates to be used in modeling. We find that first order removal kinetics for dissolution seems adequate. Based on limited data from literature, probable removal rates range from 0 to 10(-4)s(-1) for sedimentation, and from 0 to 10(-5)s(-1) for dissolution. Further experimental data at environmentally relevant conditions for sedimentation and dissolution of NMs is needed.