Samuel N. Luoma

Silver nanoparticles: Behaviour and effects in the aquatic environment

This review summarises and evaluates the present knowledge on the behaviour, the biological effects and the routes of uptake of silver nanoparticles (Ag NPs) to organisms, with considerations on the nanoparticle physicochemistry in the ecotoxicity testing systems used. Different types of Ag NP syntheses, characterisation techniques and predicted current and future concentrations in the environment are also outlined. Rapid progress in this area has been made over the last few years, but there is still a critical lack of understanding of the need for characterisation and synthesis in environmental and ecotoxicological studies. Concentration and form of nanomaterials in the environment are difficult to quantify and methodological progress is needed, although sophisticated exposure models show that predicted environmental concentrations (PECs) for Ag NPs in different environmental compartments are at the range of ng L(-1) to mg kg(-1). The ecotoxicological literature shows that concentrations of Ag NPs below the current and future PECs, as low as just a few ng L(-1), can affect prokaryotes, invertebrates and fish indicating a significant potential, though poorly characterised, risk to the environment. Mechanisms of toxicity are still poorly understood although it seems clear that in some cases nanoscale specific properties may cause biouptake and toxicity over and above that caused by the dissolved Ag ion. This review concludes with a set of recommendations for the advancement of understanding of the role of nanoscale silver in environmental and ecotoxicological research.

Bioavailability of trace metals to aquatic organisms — A review

The physiological characteristics of the environmental interface of organisms determine the metal forms of highest bioavailability. Studies of metal uptake from solution by aquatic organisms verify the high availability of free metal ions. Metals also are accumulated from food by many aquatic organisms, as indicated by both laboratory and field studies. The quantitative importance of the food vector depends upon biological availability, which differs with the specific type of food being ingested. Uptake from both food and solute vectors may be influenced by interactions among cations, pH, redox, temperature and physiological variables. Separating their relative importance through a basic understanding of these processes will be a necessary prerequisite to understanding metal impacts in natural systems.

The Modification of an Estuary

The San Francisco Bay estuary has been rapidly modified by human activity. Diking and filling of most of its wetlands have eliminated habitats for fish and waterfowl; the introduction of exotic species has transformed the composition of its aquatic communities; reduction of freshwater inflow by more than half has changed the dynamics of its plant and animal communities; and wastes have contaminated its sediments and organisms. Continued disposal of toxic wastes, the probable further reduction in freshwater inflow, and the possible synergy between the two provide the potential for further alteration of the estuarys water quality and biotic communities.

Can we determine the biological availability of sediment-bound trace elements?

It is clear from available data that the susceptibility of biological communities to trace element contamination differs among aquatic environments. One important reason is that the bioavailability of metals in sediments appears to be altered by variations in sediment geochemistry. However, methods for explaining or predicting the effect of sediment geochemistry upon metal bioavailability are poorly developed. Experimental studies demonstrate that ingestion of sediments and uptake from solution may both be important pathways of metal bioaccumulation in deposit/detritus feeding species. Relative importance between the two is geochemistry dependent. Geochemical characteristics of sediments also affect metal concentrations in the tissues of organisms collected from nature, but the specific mechanisms by which these characteristics influence metal bioavailability have not been rigorously demonstrated. Several prerequisites are necessary to better understand the processes that control metal bioavailability from sediments. 1) improved computational or analytical methods for analyzing distribution of metals among components of the sediments; 2) improved computational methods for assessing the influences of metal form in sediments on sediment-water metal exchange; and 3) a better understanding of the processes controlling bioaccumulation of metals from solution and food by metazoan species directly exposed to the sediments. Such capabilities would allow mechanistic explanations essential to the development of practical tools sought for determining sediment quality criteria for metals.

A STATISTICAL ASSESSMENT OF THE FORM OF TRACE METALS IN OXIDIZED ESTUARINE SEDIMENTS EMPLOYING CHEMICAL EXTRACTANTS

Abstract The thin layer of oxidized sediment at the sediment—water interface plays an important role in the chemical and biological interactions of trace metals in estuaries. Chemical extractants can be useful in defining trace metal interactions in sediments. Extractions may aid in determining the abundance of the operationally-defined forms of substrates which are the most active in binding metals in sediments; in operationally-defining an “extractable” phase of trace metals in sediments; and in providing information necessary for determining the bioavailability of sediment-bound metals. Comparison of 10 techniques for metal and substrate extractions among the sediments of 19 estuaries from south and west England indicate substrate characterization is best accomplished by Fe and Mn extractions with acid ammonium oxalate or 1N HCl, and humic substances extraction with 0.1N NaOH or 1N ammonia. Partial fractionation of trace metals is best accomplished with 1N HCl. Statistical relationships indicate the extractable phase of Fe is more important than total Fe in binding Ag, Cd, Cu, Pb and Zn in oxidized sediments, and the operationally-defined humic substance fraction of organic materials is highly important in binding Ag and Cu. Statistical analysis within specific subsets of data indicate trace metals are partitioned among several substrates in most sediments, the substrates compete with one another for the metals, and the outcome of the competition is strongly influenced by the concentrations of the different substrates in the sediment.

Trace element trophic transfer in aquatic organisms: A critique of the kinetic model approach

The bioaccumulation of trace elements in aquatic organisms can be described with a kinetic model that includes linear expressions for uptake and elimination from dissolved and dietary sources. Within this model, trace element trophic transfer is described by four parameters: the weight-specific ingestion rate (IR); the assimilation efficiency (AE); the physiological loss rate constant (ke); and the weight-specific growth rate (g). These four parameters define the trace element trophic transfer potential (TTP = IR.AE/[ke + g]) which is equal to the ratio of the steady-state trace element concentration in a consumer due to trophic accumulation to that in its prey. Recent work devoted to the quantification of AE and ke for a variety of trace elements in aquatic invertebrates has provided the data needed for comparative studies of trace element trophic transfer among different species and trophic levels and, in at least one group of aquatic consumers (marine bivalves), sensitivity analyses and field tests of kinetic bioaccumulation models. Analysis of the trophic transfer potentials of trace elements for which data are available in zooplankton, bivalves, and fish, suggests that slight variations in assimilation efficiency or elimination rate constant may determine whether or not some trace elements (Cd, Se, and Zn) are biomagnified. A linear, single-compartment model may not be appropriate for fish which, unlike many aquatic invertebrates, have a large mass of tissue in which the concentrations of most trace elements are subject to feedback regulation.

Historical trends of metals in the sediments of San Francisco Bay, California

Abstract Concentrations of Ag, Al, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn were determined in six sediment cores from San Francisco Bay (SFB) and one sediment core in Tomales Bay (TB), a reference estuary. SFB cores were collected from between the head of the estuary and its mouth (Grizzly Bay, GB; San Pablo Bay, SP; Central Bay, CB; Richardson Bay, RB, respectively) and ranged in length from 150 to 250 cm. Concentrations of Cr, V and Ni are greater than mean crustal content in SFB and TB sediments, and greater than found in many other coastal sediments. However, erosion of ultramafic rock formations in the watershed appears to be the predominant source. Baseline concentrations of other metals were determined from horizons deposited before sediments were influenced by human activities and by comparing concentrations to those in TB. Baseline concentrations of Cu co-varied with Al in the SFB sediments and ranged from 23.7±1.2 μg/g to 41.4±2.4 μg/g. Baseline concentrations of other metals were less variable: Ag, 0.09±0.02 μg/g; Pb, 5.2±0.7 μg/g; Hg, 0.06±0.01 μg/g; Zn, 78±7 μg/g. The earliest anthropogenic influence on metal concentrations appeared as Hg contamination (0.3–0.4 μg/g) in sediments deposited at SP between 1850 and 1880, apparently associated with debris from hydraulic gold mining. Maximum concentrations of Hg within the cores were 20 times baseline. Greater inventories of Hg at SP and GB than at RB verified the importance of mining in the watershed as a source. Enrichment of Ag, Pb, Cu and Zn first appeared after 1910 in the RB core, later than is observed in Europe or eastern North America. Maximum concentrations of Ag and Pb were 5–10 times baseline and Cu and Zn concentrations were less than three times baseline. Large inventories of Pb to the sediments in the GB and SP cores appeared to be the result of the proximity to a large Pb smelter. Inventories of Pb at RB are similar to those typical of atmospheric inputs, although influence from the Pb smelter is also suspected. Concentrations of Hg and Pb have decreased since the 1970s (to 0.30 μg/g and 25 μg/g, respectively) and were similar among all cores in 1990. Early Ag contamination was perhaps a byproduct of the Pb smelting process, but a modern source of Ag is also indicated, especially at RB and CB.

The complexity of nanoparticle dissolution and its importance in nanotoxicological studies.

Dissolution of nanoparticles (NPs) is an important property that alters their abundance and is often a critical step in determining safety of nanoparticles. The dissolution status of the NPs in exposure media (i.e. whether they remain in particulate form or dissolve - and to what extent), strongly affects the uptake pathway, toxicity mechanisms and the environmental compartment in which NPs will have the highest potential impact. A review of available dissolution data on NPs demonstrates there is a range of potential outcomes depending on the NPs and the exposure media. For example two nominally identical nanoparticles, in terms of size and composition, could have totally different dissolution behaviours, subject to different surface modifications. Therefore, it is imperative that toxicological studies are conducted in conjunction with dissolution of NPs to establish the true biological effect of NPs and hence, assist in their regulation.

Requirements for modeling trace metal partitioning in oxidized estuarine sediments

Abstract The fate of particulate-bound metals is of particular importance in estuaries because major biological energy flows involve consumption of detrital particles. The biological impact of particulate-bound metals is strongly influenced by the partitioning of metals among sediment components at the oxidized sediment—water interface. Adequate methods for directly measuring this partitioning are not available, thus a modeling approach may be most useful. Important requirements for such a model include: (1) determinations of metal binding intensities which are comparable among sediment components important in oxidized sediments; (2) comparable determinations of the binding capacities of the several forms of each component; (3) operational determinations of the abundance in natural sediments of components of defined binding capacity; (4) assessments of the influence of particle coatings and multicomponent aggregation on the available binding capacity of each substrate; (5) consideration of the effect of Ca and Mg competition on binding to different components; and (6) determinations of the kinetics of metal redistribution among components in oxidized sediments.

Sedimentary record of anthropogenic and biogenic polycyclic aromatic hydrocarbons in San Francisco Bay, California

Dated sediment cores collected from Richardson and San Pablo Bays in San Francisco Bay were used to reconstruct a history of polycyclic aromatic hydrocarbon (PAH) contamination. The sedimentary record of PAHs in Richardson Bay shows that anthropogenic inputs have increased since the turn of the century, presumably as a result of increasing urbanization and industrialization around the Bay Area. Concentrations range from about 0.04–6.3 μg g−1. The dominant origin of the PAHs contributing to this modern contamination is from combustion processes. Depth profiles in San Pablo Bay indicate higher concentrations of PAHs since the 1950s than during the late 1800s, also presumably resulting from an increase in urbanization and industrialization. Total PAHs in San Pablo Bay range from about 0.04–1.3 μg g−1. The ratios of methylphenanthrenes/phenanthrene and (methylfluoranthenes+methylpyrenes)/fluoranthene were sensitive indicators of anthropogenic influences in the estuary. Variations in the ratio of 1,7-dimethylphenanthrene/2,6-dimethylphenanthrene indicate a gradual replacement of wood by fossil-fuel as the main combustion source of PAHs in San Francisco Bay sediments. The profile of perylene may be an indicator of eroding peat from marshlands.