Graeme E. Batley

Nanomaterials in the environment: Behavior, fate, bioavailability, and effects

The recent advances in nanotechnology and the corresponding increase in the use of nanomaterials in products in every sector of society have resulted in uncertainties regarding environmental impacts. The objectives of this review are to introduce the key aspects pertaining to nanomaterials in the environment and to discuss what is known concerning their fate, behavior, disposition, and toxicity, with a particular focus on those that make up manufactured nanomaterials. This review critiques existing nanomaterial research in freshwater, marine, and soil environments. It illustrates the paucity of existing research and demonstrates the need for additional research. Environmental scientists are encouraged to base this research on existing studies on colloidal behavior and toxicology. The need for standard reference and testing materials as well as methodology for suspension preparation and testing is also discussed.

The biotic ligand model: a historical overview

During recent years, the biotic ligand model (BLM) has been proposed as a tool to evaluate quantitatively the manner in which water chemistry affects the speciation and biological availability of metals in aquatic systems. This is an important consideration because it is the bioavailability and bioreactivity of metals that control their potential to cause adverse effects. The BLM approach has gained widespread interest amongst the scientific, regulated and regulatory communities because of its potential for use in developing water quality criteria (WQC) and in performing aquatic risk assessments for metals. Specifically, the BLM does this in a way that considers the important influences of site-specific water quality. This journal issue includes papers that describe recent advances with regard to the development of the BLM approach. Here, the current status of the BLM development effort is described in the context of the longer-term history of advances in the understanding of metal interactions in the environment upon which the BLM is based. Early developments in the aquatic chemistry of metals, the physiology of aquatic organisms and aquatic toxicology are reviewed first, and the degree to which each of these disciplines influenced the development of water quality regulations is discussed. The early scientific advances that took place in each of these fields were not well coordinated, making it difficult for regulatory authorities to take full advantage of the potential utility of what had been learned. However, this has now changed, with the BLM serving as a useful interface amongst these scientific disciplines, and within the regulatory arena as well. The more recent events that have led to the present situation are reviewed, and consideration is given to some of the future needs and developments related to the BLM that are envisioned. The research results that are described in the papers found in this journal issue represent a distinct milestone in the ongoing evolution of the BLM approach and, more generally, of approaches to performing ecological assessments for metals in aquatic systems. These papers also establish a benchmark to which future scientific and regulatory developments can be compared. Finally, they demonstrate the importance and usefulness of the concept of bioavailability and of evaluative tools such as the BLM.

Fate and Risks of Nanomaterials in Aquatic and Terrestrial Environments

Over the last decade, nanoparticles have been used more frequently in industrial applications and in consumer and medical products, and these applications of nanoparticles will likely continue to increase. Concerns about the environmental fate and effects of these materials have stimulated studies to predict environmental concentrations in air, water, and soils and to determine threshold concentrations for their ecotoxicological effects on aquatic or terrestrial biota. Nanoparticles can be added to soils directly in fertilizers orplant protection products or indirectly through application to land or wastewater treatment products such as sludges or biosolids. Nanoparticles may enter aquatic systems directly through industrial discharges or from disposal of wastewater treatment effluents or indirectly through surface runoff from soils. Researchers have used laboratory experiments to begin to understand the effects of nanoparticles on waters and soils, and this Account reviews that research and the translation of those results to natural conditions. In the environment, nanoparticles can undergo a number of potential transformations that depend on the properties both of the nanoparticle and of the receiving medium. These transformations largely involve chemical and physical processes, but they can involve biodegradation of surface coatings used to stabilize many nanomaterial formulations. The toxicity of nanomaterials to algae involves adsorption to cell surfaces and disruption to membrane transport. Higher organisms can directly ingest nanoparticles, and within the food web, both aquatic and terrestrial organisms can accumulate nanoparticles. The dissolution of nanoparticles may release potentially toxic components into the environment. Aggregation with other nanoparticles (homoaggregation) or with natural mineral and organic colloids (heteroaggregation) will dramatically change their fate and potential toxicity in the environment. Soluble natural organic matter may interact with nanoparticles to change surface charge and mobility and affect the interactions of those nanoparticles with biota. Ultimately, aquatic nanomaterials accumulate in bottom sediments, facilitated in natural systems by heteroaggregation. Homoaggregates of nanoparticles sediment more slowly. Nanomaterials from urban, medical, and industrial sources may undergo significant transformations during wastewater treatment processes. For example, sulfidation of silver nanoparticles in wastewater treatment systems converts most of the nanoparticles to silver sulfides (Ag₂S). Aggregation of the nanomaterials with other mineral and organic components of the wastewater often results in most of the nanomaterial being associated with other solids rather than remaining as dispersed nanosized suspensions. Risk assessments for nanomaterial releases to the environment are still in their infancy, and reliable measurements of nanomaterials at environmental concentrations remain challenging. Predicted environmental concentrations based on current usage are low but are expected to increase as use increases. At this early stage, comparisons of estimated exposure data with known toxicity data indicate that the predicted environmental concentrations are orders of magnitude below those known to have environmental effects on biota. As more toxicity data are generated under environmentally-relevant conditions, risk assessments for nanomaterials will improve to produce accurate assessments that assure environmental safety.

Adsorption as a control of metal concentrations in sediment extracts

w The adsorption of Cu, Pb, and Cd from selected extractant solutions, onto uncontaminated river sediments, has been investigated under typical extraction conditions. Significant adsqrption of added metal was found to occur during overnight extraction with dilute HC1 (pH >1.5), 0.1 M hydroxylamine hydrochloride (pH 2), 0.1 M sodium citrate (pH 4.6), 1 M ammonium acetate, 10% sodium citrate-1% sodium dithionite, and 25% acetic acid. Adsorption also occurred during a hydrogen peroxide digestion procedure. The inability of reagents to prevent losses of soluble metal in these experiments strongly suggests that a proportion of the metal actually released from a sediment sample during an extraction will be readsorbed. This may lead to serious misinterpretation of extraction data because the metal concentrations determined in the extract do not represent metal levels in the sediment fractions attacked.

Physico-chemical behaviour and algal toxicity of nanoparticulate CeO2 in freshwater

In assessing the risks posed by nanomaterials in the environment, the overriding research challenges are to determine if nanomaterials are more toxic than the bulk forms of the same material, and the extent to which toxicity is governed by particle size and reactivity. In this study, the toxicity of nanoparticulate CeO2 (nominally 10-20 nm) to the freshwater alga Pseudokirchneriella subcapitata was compared to the same material at the micron size (nominally <5 µm). Growth inhibition experiments revealed inhibitory concentration values, giving 50% reduction in algal growth rate after 72 h (IC50), of 10.3 ± 1.7 and 66 ± 22 mg L −1 for the nanoparticles and bulk materials respectively. Cells exposed to CeO2 particles were permeable to the DNA-binding dye SYTOX ® Green in a concentration-dependent manner indicating damage to the cell membrane. Screening assays to assess the oxidative activity of the particles showed that the light illumination conditions used during standard assays are sufficient to stimulate photocatalytic activity of CeO2 particles, causing the generation of hydroxyl radicals and peroxidation of a model plant fatty acid. No oxidative activity or lipid peroxidation was observed in the dark. These findings indicate that inhibitory mode of action of CeO2 to P. subcapitata is mediated by a cell-particle interaction causing membrane damage. The effect is most likely photochemically induced and is enhanced for the nanoparticulate form of the CeO2.

Speciation and Bioavailability of Trace Metals in Water: Progress Since 1982

The advances in studies of trace metal speciation and bioavailability since Mark Florence’s 1982 review of the topic, published in Talanta, have been comprehensively reviewed. While the relative merits of kinetic and equilibrium approaches are still being determined, advances in the applications of stripping voltammetry, including the application of microelectrodes and an appreciation of detection windows in both CSV and ASV, have been matched by the introduction of new dynamic techniques including diffusive gradients in thin films (DGTs), permeation liquid membranes (PLMs), and improved applications of chelating resins. There have also been improvements in equilibrium techniques such as ion-selective electrodes and Donnan dialysis. The ability of geochemical speciation models to predict metal complexation by natural organic matter has greatly improved, yet the models still require validation against field measurements. More reliable and relevant bioassays have been developed using sensitive species such as algae and bacteria, and improved protocols are eliminating uncertainties particularly due to problems with high cell densities, and are allowing more useful comparisons with chemically estimated bioavailability. While the free-ion activity model has provided an improved interpretation of the relative toxicities observed with different metal species, its extension to the biotic ligand model is leading to better predictions of acute effects at least on higher organisms. The extension of such approaches to studies of chronic effects at ‘natural’ concentrations using unicellular organisms remains a challenge, as does the evaluation of whether such approaches are simplified limiting cases of a more dynamic natural situation where chemical reactivity and rates of metal transport could be important.

A Weight-of-Evidence Framework for Assessing Sediment (Or Other) Contamination: Improving Certainty in the Decision-Making Process

A basic framework is presented for the ecological weight-of-evidence (WOE) process for sediment assessment that clearly defines its essential elements and will improve the certainty of conclusions about whether or not impairment exists due to sediment contamination, and, if so, which stressors and biological species (or ecological responses) are of greatest concern. The essential “Certainty Elements” are addressed in a transparent best professional judgment (BPJ) process with multiple lines-of-evidence (LOE) ultimately quantitatively integrated (but not necessarily combined into a single value). The WOE Certainty Elements include: (1) Development of a conceptual model (showing linkages of critical receptors and ecosystem quality characteristics); (2) Explanation of linkages between measurement endpoint responses (direct and indirect with associated spatial/temporal dynamics) and conceptual model components; (3) Identification of possible natural and anthropogenic stressors with associated exposure dynamics; (4) Evaluation of appropriate and quantitatively based reference (background) comparison methods; (5) Consideration of advantages and limitations of quantification methods used to integrate LOE; (6) Consideration of advantages and limitations of each LOE used; (7) Evaluation of causality criteria used for each LOE during output verification and how they were implemented; and (8) Combining the LOE into a WOE matrix for interpretation, showing causality linkages in the conceptual model. The framework identifies several statistical approaches for integrating within LOE, the suitability of which depends on physical characteristics of the system and the scale/nature of impairment. The quantification approaches include: (1) Gradient (regression methods); (2) Paired reference/test (before/after control impact and ANOVA methods); (3) Multiple reference (ANOVA and multivariate methods); and 4) Gradient with reference (regression, ANOVA and multivariate methods). This WOE framework can be used for any environmental assessment and is most effective when incorporated into the initial and final study design stages (e.g., the Problem Formulation and Risk Characterization stages of a risk assessment) with reassessment throughout the project and decision-making process, rather than in a retrospective data analysis approach where key certainty elements cannot be adequately addressed.

The impact of size on the fate and toxicity of nanoparticulate silver in aquatic systems

The increased use of silver nanomaterials presents a risk to aquatic systems due to the high toxicity of silver. The stability, dissolution rates and toxicity of citrate- and polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) were investigated in synthetic freshwater and natural seawater media, with the effects of natural organic matter investigated in freshwater. When sterically stabilised by the large PVP molecules, AgNPs were more stable than when charge-stabilised using citrate, and were even relatively stable in seawater. In freshwater and seawater, citrate-coated AgNPs (Ag-Cit) had a faster rate of dissolution than PVP-coated AgNPs (Ag-PVP), while micron-sized silver exhibited the slowest dissolution rate. However, similar dissolved silver was measured for both AgNPs after 72h in freshwater (500-600μgL(-1)) and seawater (1300-1500μgL(-1)), with higher concentrations in seawater attributed to chloride complexation. When determined on a mass basis, the 72-h IC50 (inhibitory concentration giving 50% reduction in algal growth rate) for Pseudokirchneriella subcapitata and Phaeodactylum tricornutum and the 48-h LC50 for Ceriodaphnia dubia exposure to Ag(+) (1.1, 400 and 0.11μgL(-1), respectively), Ag-Cit (3.0, 2380 and 0.15μgL(-1), respectively) and Ag-PVP (19.5, 3690 and 2.0μgL(-1), respectively) varied widely, with toxicity in the order Ag(+)>Ag-Cit>Ag-PVP. Micron-sized silver treatments elicited much lower toxicity than ionic Ag(+) or AgNP to P. subcapitata. However, when related to the dissolved silver released from the nanoparticles the toxicities were similar to ionic silver treatments. The presence of natural organic matter stabilised the particles and reduced toxicity in freshwater. These results indicate that dissolved silver was responsible for the toxicity and highlight the need to account for matrix components such as chloride and organic matter in natural waters that influence AgNP fate and mitigate toxicity.

The influence of sediment particle size and organic carbon on toxicity of copper to benthic invertebrates in oxic/suboxic surface sediments

The use of sediment quality guidelines to predict the toxicity of metals in sediments is limited by an inadequate understanding of exposure pathways and by poor causal links between exposure and effects. For a 10-d exposure to Cu-spiked sediments, toxicity to the amphipod Melita plumulosa was demonstrated to occur through a combination of dissolved and dietary Cu exposure pathways, but for the bivalves Spisula trigonella and Tellina deltoidalis, toxicity occurred primarily by exposure to dissolved Cu. For relatively oxidized sediments that had moderate amounts of organic carbon (2.6-8.3% OC), silt (20-100% <63-µm particles) but low acid-volatile sulfide (AVS), acute toxicity thresholds for the three species were derived based on the OC-normalized Cu concentration of the less than 63-µm sediment fraction. For all three species, no effects were observed at concentrations below 10 µg/L dissolved Cu (in pore water and overlying water) or below 12 mg Cu/g OC (for <63 µm sediment). For sediments with silt/OC properties of 20/0.5, 50/1, or 70/4%, the particulate Cu-based threshold equated to 60, 120, or 480 mg Cu/kg, respectively. For oxic/suboxic sediments in which AVS is not limiting metal availability, sediment quality guidelines of this form will provide adequate protection against toxicity and improve the prediction of effects for sediments with varying properties.

Pore water sampling with sediment peepers

Abstract The use of in situ equilibrium dialysis samplers (peepers) for the collection of sediment pore waters for trace metal analysis is reviewed. Optimum peeper designs, construction and preparation procedures are described. Field deployment and sampling protocols are outlined with their utility illustrated by dissolved metal profiles obtained from field studies.