Environmental Toxicology and Chemistry

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.

Ecological risk assessors face increasing demands to assess more chemicals, with greater speed and accuracy, and to do so using fewer resources and experimental animals. New approaches in biological and computational sciences may be able to generate mechanistic information that could help in meeting these challenges. However, to use mechanistic data to support chemical assessments, there is a need for effective translation of this information into endpoints meaningful to ecological risk—effects on survival, development, and reproduction in individual organisms and, by extension, impacts on populations. Here we discuss a framework designed for this purpose, the adverse outcome pathway (AOP). An AOP is a conceptual construct that portrays existing knowledge concerning the linkage between a direct molecular initiating event and an adverse outcome at a biological level of organization relevant to risk assessment. The practical utility of AOPs for ecological risk assessment of chemicals is illustrated using five case examples. The examples demonstrate how the AOP concept can focus toxicity testing in terms of species and endpoint selection, enhance across‐chemical extrapolation, and support prediction of mixture effects. The examples also show how AOPs facilitate use of molecular or biochemical endpoints (sometimes referred to as biomarkers) for forecasting chemical impacts on individuals and populations. In the concluding sections of the paper, we discuss how AOPs can help to guide research that supports chemical risk assessments and advocate for the incorporation of this approach into a broader systems biology framework. Environ. Toxicol. Chem. 2010;29:730–741. © 2009 SETAC

It is becoming evident that an increasing number of widely used industrial and agricultural chemicals are estrogenic. The biodegradation products of a major group of nonionic surfactants, the alkylphenol polyethoxylates, are one such group. Some of these chemicals are widespread aquatic pollutants, and bioconcentrate in aquatic biota. Exposure of male rainbow trout (Oncorhynchus mykiss) to four different alkylphenolic chemicals caused synthesis of vitellogenin, a process normally dependent on endogenous estrogens, and a concomitant inhibition of testicular growth. The magnitude of these estrogenic effects was dependent on the estrogenic potency of the chemical, the stage of reproductive development of the fish, and the concentration of the chemical in the water. These results support the contention that exposure of wildlife to environmentally persistent estrogenic chemicals can result in deleterious reproductive consequences.

A eview of the literature revealed that bioaccumulation of silver in soil is rather low, even if the soil is amended with silver‐containing sewage sludge. Plants grown on tailings of silver mines were found to have silver primarily in the root systems. In marine and freshwater systems, the highest reported bioconcentration factors (BCFs) were observed in algae (>10⁵), probably because of adsorption of the dissolved silver (<0.45 μm fraction) to the cell surface. In herbivorous organisms (e.g., zooplankton and bivalves), the BCF was lower by about two orders of magnitude. Low amounts of silver were assimilated from food with no substantial biomagnification. In carnivores (e.g., fish), the BCF was also lower by one order of magnitude with no indication of biomagnification. Toxicity of silver occurs mainly in the aqueous phase and depends on the concentration of active, free Ag⁺ions. Accordingly, many processes and water characteristics reduce silver toxicity by stopping the formation of free Ag⁺, binding Ag⁺, or preventing binding of Ag⁺to the reactive surfaces of organisms. The solubility of a silver compound, and the presence of complexing agents (e.g., thiosulfate or chloride), dissolved organic carbon, and competing ions are important. In soil, sewage sludge, and sediments, in which silver sulfide predominates, the toxicity of silver, even at high total concentrations, is very low. The highly soluble silver thiosulfate complex has low toxicity, which can be attributed to the silver complexed by thiosulfate. Silver nitrate is one of the most toxic silver compounds. The toxic potential of silver chloride complexes in seawater is and will be an important issue for investigation. Aquatic chronic tests, long‐term tests, and tests including sensitive life stages show lower toxicity thresholds (˜1 μg Ag⁺/L). The organisms viewed as most sensitive to silver are small aquatic invertebrates, particularly embryonic and larval stages.

A battery of biomarkers is often used to evaluate the effects of exposure to chemical contaminants and detect responses to environmental stress. Unfortunately, field application of biomarkers is subject to various constraints (e.g., the availability of living material) that can limit data acquisition and prevent the use of multivariate methods during statistical analysis. In these circumstances, a simple method is needed to summarize biomarker responses and simplify their interpretation in biomonitoring programs. The present study used star plots to display results for the panel of biomarkers used for each station and survey. Integrated biomarker response (IBR) was then computed as the star plot area. Star plots using IBR values instead of biomarker data make it possible to visualize between‐site and/or between‐survey differences for comparison with exposure conditions. This approach was applied to sites in the Baltic Sea and the Seine Estuary, English Channel. In both cases, IBR values were visually compared to polycyclic aromatic hydrocarbons (PAH) or polychlorobiphenyls (PCB) levels measured in mussel or fish tissues. The IBR, as an indicator of environmental stress, appears to be a useful tool for scientists and managers in assessing ecological risk.

Low levels of pharmaceuticals are detected in surface, ground, and drinking water worldwide. Usage and incorrect disposal have been considered the major environmental sources of these microcontaminants. Recent publications, however, suggest that wastewater from drug production can potentially be a source of much higher concentrations in certain locations. The present study investigated the environmental fate of active pharmaceutical ingredients in a major production area for the global bulk drug market. Water samples were taken from a common effluent treatment plant near Hyderabad, India, which receives process water from approximately 90 bulk drug manufacturers. Surface water was analyzed from the recipient stream and from two lakes that are not contaminated by the treatment plant. Water samples were also taken from wells in six nearby villages. The samples were analyzed for the presence of 12 pharmaceuticals with liquid chromatography‐mass spectrometry. All wells were determined to be contaminated with drugs. Ciprofloxacin, enoxacin, cetirizine, terbinafine, and citalopram were detected at more than 1 μg/L in several wells. Very high concentrations of ciprofloxacin (14 mg/L) and cetirizine (2.1 mg/L) were found in the effluent of the treatment plant, together with high concentrations of seven additional pharmaceuticals. Very high concentrations of ciprofloxacin (up to 6.5 mg/L), cetirizine (up to 1.2 mg/L), norfloxacin (up to 0.52 mg/L), and enoxacin (up to 0.16 mg/L) were also detected in the two lakes, which clearly shows that the investigated area has additional environmental sources of insufficiently treated industrial waste. Thus, insufficient wastewater management in one of the world's largest centers for bulk drug production leads to unprecedented drug contamination of surface, ground, and drinking water. This raises serious concerns regarding the development of antibiotic resistance, and it creates a major challenge for producers and regulatory agencies to improve the situation.

In this paper a novel multivariate method is proposed for the analysis of community response data from designed experiments repeatedly sampled in time. The long‐term effects of the insecticide chlorpyrifos on the invertebrate community and the dissolved oxygen (DO)–pH–alkalinity–conductivity syndrome, in outdoor experimental ditches, are used as example data. The new method, which we have named the principal response curve method (PRC), is based on redundancy analysis (RDA), adjusted for overall changes in community response over time, as observed in control test systems. This allows the method to focus on the time‐dependent treatment effects. The principal component is plotted against time, yielding a principal response curve of the community for each treatment. The PRC method distills the complexity of time‐dependent, community‐level effects of pollutants into a graphic form that can be appreciated more readily than the results of other currently available multivariate techniques. The PRC method also enables a quantitative interpretation of effects towards the species level.

Government agencies at both the state and federal levels now face increasing pressures to assess the likelihood of pesticide occurrence in well‒water supplies. Screening methodologies are required in order to determine which pesticides now in use should receive the greatest attention with respect to groundwater, and in order to determine whether elaborate and expensive groundwater testing should be required in order to register a new pesticide. Several screening techniques have been proposed recently, some based on threshold values for critical physical properties of the pesticide, and others based on mathematical models of the leaching process. A different approach is taken in this paper, whereby an index is derived based entirely on the physical properties of those pesticides that have been found either leachable or essentially immobile. The index is based on graphical examination of a plot formed by two widely available pesticide properties: half‒life in soil (t^soil_1/2) and partition coefficient between soil organic carbon and water (K_oc). Other physical properties, such as water solubility, octanol/water partition coefficient, and volatility from soil, have often been invoked as indicators of leachability, but they are found in this paper to have no useful power in discriminating between “leachers” and “nonleachers.” Scores assigned with the new screening index agree with the results of several recent well‒water monitoring programs, even though point‒source events are thought to be responsible for some of the observed contamination. A nomogram is given that reduces the task of calculating the index to simply placing a straight edge on a diagram.

The distribution of polycyclic aromatic hydrocarbons (PAHs) has been investigated in superficial sediments and mussels (Mytilus galloprovincialis) of the western Mediterranean sea (French Riviera, Corsica, Sardinia). The analyses were performed by gas chromatography coupled to mass spectrometry (GC‐MS). The PAH concentrations ranged from 1 to 20,500 ng/g in the sediments. Different molecular indices allowed differentiation between the different pollutant sources. On the French coast, PAHs originated mainly from incomplete combustion of organic matter (pyrolytic origin), whereas for some sites in Corsica and Sardinia an overimposition of petrogenic PAHs occurred. The mussel PAH concentrations ranged from 25 to 390 ng/g. The total and individual PAH bioaccumulation factors were calculated. The correlation between sediment and mussel PAH content was discussed in terms of bioavailability. It was possible to distinguish different absorption routes for the xenobiotics according to their physicochemical properties. Because the mussel distribution of phenanthrene and anthracene seems to be governed by their water solubility, these compounds were probably mainly absorbed as the water‐dissolved form, whereas the heavier molecular weight PAHs (more than four aromatic rings), whose sediment and mussel concentrations are correlated with higher correlation coefficients than for phenanthrene and anthracene, were probably mainly absorbed as adsorbed on particles. Furthermore, a possible preferential biotransformation of benzo[a]pyrene over benzo[e]pyrene is discussed.