Showing papers in "Environmental Toxicology and Chemistry in 2008"
TL;DR: This review critiques existing nanomaterial research in freshwater, marine, and soil environments and illustrates the paucity of existing research and demonstrates the need for additional research.
Abstract: 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.
2,566 citations
TL;DR: The results indicate that nanosilver and nanocopper causeoxicity in all organisms tested, with 48-h median lethal concentrations as low as 40 and 60 microg/L, respectively, in Daphnia pulex adults, whereas titanium dioxide did not cause toxicity in any of the tests.
Abstract: Metallic nanoparticles are among the most widely used types of engineered nanomaterials; however, little is known about their environmental fate and effects. To assess potential environmental effects of engineered nanometals, it is important to determine which species are sensitive to adverse effects of various nanomaterials. In the present study, zebrafish, daphnids, and an algal species were used as models of various trophic levels and feeding strategies. To understand whether observed effects are caused by dissolution, particles were characterized before testing, and particle concentration and dissolution were determined during exposures. Organisms were exposed to silver, copper, aluminum, nickel, and cobalt as both nanoparticles and soluble salts as well as to titanium dioxide nanoparticles. Our results indicate that nanosilver and nanocopper cause toxicity in all organisms tested, with 48-h median lethal concentrations as low as 40 and 60 μg/L, respectively, in Daphnia pulex adults, whereas titanium dioxide did not cause toxicity in any of the tests. Susceptibility to nanometal toxicity differed among species, with filter-feeding invertebrates being markedly more susceptible to nanometal exposure compared with larger organisms (i.e., zebrafish). The role of dissolution in observed toxicity also varied, being minor for silver and copper but, apparently, accounting for most of the toxicity with nickel. Nanoparticulate forms of metals were less toxic than soluble forms based on mass added, but other dose metrics should be developed to accurately assess concentration–response relationships for nanoparticle exposures.
851 citations
TL;DR: In this paper, the effect of Cu nanoparticles on the growth of a plant seedling was studied, and bioaccumulation of nanoparticles was investigated in plant agar media to prevent precipitation of water-insoluble nanoparticles.
Abstract: Because of their insolubility in water, nanoparticles have a limitation concerning toxicity experiments. The present study demonstrated a plant agar test for homogeneous exposure of nanoparticles to plant species. The effect of Cu nanoparticles on the growth of a plant seedling was studied, and bioaccumulation of nanoparticles was investigated. All tests were conducted in plant agar media to prevent precipitation of water-insoluble nanoparticles in test units. The plant species were Phaseolus radiatus (mung bean) and Triticum aestivum (wheat). Growth inhibition of a seedling exposed to different concentrations of Cu nanoparticles was examined. Copper nanoparticles were toxic to both plants and also were bioavailable. The 2-d median effective concentrations for P. radiatus and T. aestivum exposed to Cu nanoparticles were 335 (95% confidence level, 251-447) and 570 (450-722) mg/L, respectively. Phaseolus radiatus was more sensitive than T. aestivum to Cu nanoparticles. A cupric ion released from Cu nanoparticles had negligible effects in the concentration ranges of the present study, and the apparent toxicity clearly resulted from Cu nanoparticles. Bioaccumulation increased with increasing concentration of Cu nanoparticles, and agglomeration of particles was observed in the cells using transmission-electron microscopy-energy-dispersive spectroscopy. The present study demonstrated that the plant agar test was a good protocol for testing the phytotoxicity of nanoparticles, which are hardly water soluble.
610 citations
TL;DR: Nonfunctionalized and nonfunctionalized single-walled carbon nanotubes affected root length more than functionalized nanot tubes and inhibited root elongation in lettuce and tomato, respectively.
Abstract: Single-walled carbon nanotubes have many potential beneficial uses, with additional applications constantly being investigated Their unique properties, however, create a potential concern regarding toxicity, not only in humans and animals but also in plants To help develop protocols to determine the effects of nanotubes on plants, we conducted a pilot study on the effects of functionalized and nonfunctionalized single-walled carbon nanotubes on root elongation of six crop species (cabbage, carrot, cucumber, lettuce, onion, and tomato) routinely used in phytotoxicity testing Nanotubes were functionalized with poly-3-aminobenzenesulfonic acid Root growth was measured at 0, 24, and 48 h following exposure Scanning-electron microscopy was used to evaluate potential uptake of carbon nanotubes and to observe the interaction of nanotubes with the root surface In general, nonfunctionalized carbon nanotubes affected root length more than functionalized nanotubes Nonfunctionalized nanotubes inhibited root elongation in tomato and enhanced root elongation in onion and cucumber Functionalized nanotubes inhibited root elongation in lettuce Cabbage and carrots were not affected by either form of nanotubes Effects observed following exposure to carbon nanotubes tended to be more pronounced at 24 h than at 48 h Microscopy images showed the presence of nanotube sheets on the root surfaces, but no visible uptake of nanotubes was observed
390 citations
TL;DR: The interactions between unpurified manufactured nanoparticles (NPs; iron oxide NPs) and standard Suwannee River humic acid (SRHA) were investigated under a range of environmentally relevant conditions and the structure and aggregation mechanism of these aggregates were found to be both pH and SRHA concentration dependent.
Abstract: The interactions between unpurified manufactured nanoparticles (NPs; iron oxide NPs, approximately 7 nm) and standard Suwannee River humic acid (SRHA) were investigated under a range of environmentally relevant conditions. At low pH, approximately 35% of the total iron was in the dissolved phase (< 1 kDa), present from the initial synthesis, whereas at pH more than 4, this concentration was negligible because of the formation of new particles via hydrolysis. Dynamic light scattering results indicated that extensive aggregation of NPs began at approximately pH 5 to 6 and reached a maximum at approximately pH 8.5, whereas with added SRHA, aggregation was shifted to lower pH values of 4 to 5 and was affected by SRHA concentration. Aggregation could be explained mainly by charge neutralization. Further, more detailed investigations by flow field-flow fractionation and transmission-electron microscopy were performed under a more restricted set of conditions (pH 2-6) to examine the aggregation process. Results indicated the formation of SRHA surface coating on iron oxide NPs of approximately 1 nm and the increase in thickness of this coating with the increase of SRHA concentration. Iron oxide NPs were shown to form increasingly large aggregates with increases in both pH (from 2 to 6) and SRHA concentration (from 0 to 25 mg/L). The structure and aggregation mechanism of these aggregates were found to be both pH and SRHA concentration dependent, with open, porous aggregates in the absence of SRHA and compact aggregates in the presence of SRHA.
361 citations
TL;DR: It is demonstrated that fish serum could sensitively reflect environmental metal stress, and it suggests that serum biochemical parameters could be used as important and sensitive biomarkers in ecotoxicological studies concerning the effects of metal contamination and fish health.
Abstract: Fish serum may reflect status of many biochemical processes in the metabolism. Heavy metals, as environmental stressors, may alter serum biochemical parameters in fishes. Thus, freshwater fish, Oreochromis niloticus, were exposed to low levels (0.05 mg/L) of metals (silver [Ag], cadmium [Cd], copper [Cu], chromium [Cr], zinc [Zn]) to investigate responses of serum biochemical parameters over different exposure periods (0, 5, 10, 20, 30 d). Fish mortality occurred only in Ag exposure, as all fish died between days 12 to 16. Activities of alkaline phosphatase (ALP), alanine transaminase (ALT), and aspartate transaminase (AST) were altered only in Cu- and Cd-exposed fish. Both Cd and Cu exposures decreased the activity of ALP, although they increased the activities of ALT and AST. Glucose concentrations increased in Ag-, Cd-, and Cu-exposed fish, with a sharp increase occurring in Ag-exposed fish before mortality began. Total protein and triglyceride concentrations increased in Ag-exposed fish, although they decreased in Cu-exposed ones. However, all metal exposures increased cholesterol concentration in the serum. Concentration of blood urea nitrogen increased in Ag-, Cd-, and Cu-exposed fish, although it decreased in Cr-exposed ones. Calcium level decreased only in Cu-exposed fish, and Cl(-) level decreased in Ag-exposed fish. Silver and Cu exposures also decreased Na(+) level in the serum. Cadmium and Cu exposures increased serum K(+) levels. The present study, investigating the effects of environmentally realistic metal exposures on serum biochemical parameters, demonstrated that fish serum could sensitively reflect environmental metal stress. Thus, it suggests that serum biochemical parameters could be used as important and sensitive biomarkers in ecotoxicological studies concerning the effects of metal contamination and fish health.
223 citations
TL;DR: The hypothesis that the ecotoxicity of nanoparticles (NPs) is related to their surface area and not to their mass was tested using a freshwater green algal species and toxicity was found to be attributable to the solid nanospheres.
Abstract: To date, (eco)toxicological information on industrial nanoparticles is very limited. In the present study, the hypothesis that the ecotoxicity of nanoparticles (NPs) is related to their surface area and not to their mass was tested using a freshwater green algal species. Particle diameter and morphology were assessed using light scattering and electron microscopy techniques. To assess the toxicity of silica (SiO2) nanoparticles, the growth inhibition of the alga Pseudokirchneriella subcapitata when exposed to stable silica suspensions was monitored. Commercial LUDOX suspensions of nanoparticles with 12.5 and 27.0 nm diameter were found to be toxic, with 72-h 20% effect concentrations for growth rate (E(r)C20) values +/- standard deviation (n = 5) of 20.0 +/- 5.0 and 28.8 +/- 3.2 mg/L, respectively. The toxicity was attributable to the solid nanospheres, because no aggregation was observed and dissolution of the nanoparticles was negligible. When expressing the concentration as a surface area, the difference in toxicity was not significant. In the latter case, 72-h E(r)C20 values +/- standard deviation (n = 5) were 4.7 +/- 1.2 and 3.9 +/- 0.4 m2/L. Silica bulk material was found to be nontoxic up to 1 g/L. In an additional experiment with 100 mg/L of 12.5 and 27.0 nm SiO2 NPs, the interaction between the nanoparticles and algal cells was studied using transmission electron microscopy. Although the particles clearly adhered to the outer cell surface, no evidence was found for particle uptake.
218 citations
TL;DR: Degradation of decabromodiphenyl ether was observed in both matrices but was 35% greater in the spiked dust relative to the natural dust material, and the ratio of BDE 197 to BDE 201 may also be indicative of Bde 209 degradation.
Abstract: Photolytic degradation of decabromodiphenyl ether (BDE 209) has been observed in several matrices such as solvent/ water mixtures, sediments, and soil; however, no studies have investigated the degradation potential of BDE 209 in house dust. In the present study, both a natural and a BDE 209-spiked dust material were exposed to sunlight for 200 cumulative h. Degradation of BDE 209 was observed in both matrices but was 35% greater in the spiked dust relative to the natural dust material. The pseudo- first-order degradation rates were 2.3 x 10(-3) and 1.7 x 10(-3) per hour for the spiked and natural dust, respectively. During the 200-h exposure, as much as 38% of the original BDE 209 mass was degraded in the spiked dust, 25% of which could not be accounted for and was lost to unknown pathways and/or products. The remaining 13% was accounted for by the formation of lower brominated congeners. Debrominated products detected in the spiked dust included all three nonabrominated congeners (BDE 206, BDE 207, and BDE 208) and several octabrominated congeners (BDE 196, BDE 197, BDE 201, BDE 202, and BDE 203/200). In technical commercial octa-BDE mixtures, BDE 201 is a very small component (below detection limit to 0.8%), and BDE 202 is not detected. Therefore, the presence of these congeners in house dust may provide a marker of environmental debromination of BDE 209. The ratio of BDE 197 to BDE 201 may also be indicative of BDE 209 degradation. as the ratio of these two congeners appeared to reach a steady-state value (~1) in both exposure scenarios in the present study.
214 citations
TL;DR: It may be inappropriate to classify all NTs into one category in terms of their environmental regulation, and column stability and settling experiments indicated that raw, multiwalled NTs (MWNTs) settled more rapidly than carbon black and activated carbon particles, suggesting sediment as the ultimate repository.
Abstract: Carbon nanotubes (NTs) may be among the most useful engineered nanomaterials for structural applications but could be difficult to study in ecotoxicological evaluations using existing tools relative to nanomaterials with a lower aspect ratio. Whereas the hydrophobicity and van der Waals interactions of NTs may suggest aggregation and sedimentation in aquatic systems, consideration regarding how engineered surface modifications influence their environmental fate and toxicology is needed. Surface modifications (e.g., functional groups and coatings) are intended to create conditions to make NTs dispersible in aqueous suspension, as required for some applications. In the present study, column stability and settling experiments indicated that raw, multiwalled NTs (MWNTs) settled more rapidly than carbon black and activated carbon particles, suggesting sediment as the ultimate repository. The presence of functional groups, however, slowed the settling of MWNTs (increasing order of stability: hydroxyl > carboxyl > raw), especially in combination with natural organic matter (NOM). Stabilized MWNTs in high concentrations of NOM provided relevance for water transport and toxicity studies. Aqueous exposures to raw MWNTs decreased Ceriodaphnia dubia viability, but such effects were not observed during exposure to functionalized MWNTs (> 80 mg/L). Sediment exposures of the amphipods Leptocheirus plumulosus and Hyalella azteca to different sizes of sediment-borne carbon particles at high concentration indicated mortality increased as particle size decreased, although raw MWNTs induced lower mortality (median lethal concentration [LC50], 50 to >264 g/kg) than carbon black (LC50, 18-40 g/kg) and activated carbon (LC50, 12-29 g/kg). Our findings stress that it may be inappropriate to classify all NTs into one category in terms of their environmental regulation.
188 citations
TL;DR: The results further support TCC, TCS, and MTCS as good candidate marker compounds for evaluation of environmental distribution of trace WWTP contaminants.
Abstract: Grazing by freshwater snails promotes nutrient turnover in algal communities. Grazed algal compartments may include antimicrobial agents and metabolites, such as triclocarban (TCC), triclosan (TCS), and methyltriclosan (MTCS), which are incompletely removed by wastewater treatment plant (WWTP) processing. The present study quantifies snail bioaccumulation factors (BAFs) for TCC, TCS, and MTCS at the outfall of Pecan Creek (TX, USA), the receiving stream for the city of Denton (TX, USA) WWTP. Helisoma trivolvis (Say) is ubiquitous and thrives under standard laboratory conditions, leading to its choice for this bioaccumulation study in conjunction with Cladophora spp. Along with providing substrate for epiphytic growth, Cladophora spp. provide a source of food and shelter for H. trivolvis. After being caged for two weeks, algae and snails were collected from the WWTP outfall, along with water-column samples, and analyzed by isotope dilution gas chromatography-mass spectrometry for TCS and MTCS and by liquid chromatography-mass spectrometry for TCC. Algal and snail samples were analyzed before exposure and found to be below practical quantitation limits for all antimicrobial agents. Triclocarban, TCS, and MTCS in water samples were at low-ppt concentrations (40–200 ng/L). Triclocarban, TCS, and MTCS were elevated to low-ppb concentrations (50–300 ng/g fresh wt) in caged snail samples and elevated to low-ppb concentrations (50–400 ng/g fresh wt) in caged algal samples. Resulting snail and algal BAFs were approximately three orders of magnitude, which supports rapid bioaccumulation among algae and adult caged snails at this receiving stream outfall. The results further support TCC, TCS, and MTCS as good candidate marker compounds for evaluation of environmental distribution of trace WWTP contaminants.
188 citations
TL;DR: Assessment of effects of short-term (24-h) exposure to the neonicotinoid insecticide thiacloprid, including a postexposure observation period found delayed lethal and sublethal effects, which were observed after 4 to 12 d following exposure.
Abstract: Ecotoxicological risk assessment of contaminants often is based on toxicity tests with continuous-exposure profiles. However, input of many contaminants (e.g., insecticides) to surface waters typically occurs in pulses rather than continuously. Neonicotinoids are a new group of insecticides, and little is known about their toxicity to nontarget freshwater organisms and potential effects on freshwater ecosystems. The aim of the present research was to assess effects of short-term (24-h) exposure to the neonicotinoid insecticide thiacloprid, including a postexposure observation period. A comparison of several freshwater insect and crustacean species showed an increase of sensitivity by three orders of magnitude in the following order: Daphnia magna 50-fold. Hence, delayed effects occurring after short-term exposure should be considered in risk assessment. The 5% hazardous concentration (HC5) of thiacloprid obtained in the present study (0.72 μg/L) is more than one order of magnitude below the currently predicted worst-case environmental concentrations in surface water. Concerning the selection of test organisms, we observed that the widely employed test organism D. magna is least sensitive among the arthropods tested and that, for neonicotinoid insecticides, an insect like the mosquito C. pipiens would be more suitable for predicting effects on sensitive species.
TL;DR: It is argued that population modeling can add value to ecological risk assessment by reducing uncertainty when extrapolating from ecotoxicological observations to relevant ecological effects and by incorporating greater levels of ecological complexity.
Abstract: We argue that population modeling can add value to ecological risk assessment by reducing uncertainty when extrapolating from ecotoxicological observations to relevant ecological effects. We review other methods of extrapolation, ranging from application factors to species sensitivity distributions to suborganismal (biomarker and "-omics") responses to quantitative structure-activity relationships and model ecosystems, drawing attention to the limitations of each. We suggest a simple classification of population models and critically examine each model in an extrapolation context. We conclude that population models have the potential for adding value to ecological risk assessment by incorporating better understanding of the links between individual responses and population size and structure and by incorporating greater levels of ecological complexity. A number of issues, however, need to be addressed before such models are likely to become more widely used. In a science context, these involve challenges in parameterization, questions about appropriate levels of complexity, issues concerning how specific or general the models need to be, and the extent to which interactions through competition and trophic relationships can be easily incorporated.
TL;DR: It is concluded that the absence of ecotoxicity is the result of low concentrations of free nanoparticle in the tests, and it is suggested that colloid (in)stability is of primary importance in explaining ecotoxic effects of nanoparticles in the natural environment.
Abstract: Nanoparticles of TiO2, ZrO2, AL2O3, CeO2, fullerene (C60), single-walled carbon nanotubes, and polymethylmethacrylate were tested for ecotoxic effects using one or more ecotoxicity endpoints: Microtox (bacteria), pulse-amplitude modulation (algae), Chydotox (crustaceans), and Biolog (soil enzymes). No appreciable effects were observed at nominal concentrations of up to 100 mg/L. Dilution of nanoparticle suspensions, either in ultrapure (Milli-Q) water or in natural (pond) water, led to formation of larger particles, which settled easily. (Nano)particles in water were characterized by means of atomic force microscopy, energy-dispersive x-ray analysis, inductively coupled plasma-mass spectrometry, flow cytometry, and spectrophotometry. It is concluded that the absence of ecotoxicity is the result of low concentrations of free nanoparticles in the tests, and it is suggested that colloid (in)stability is of primary importance in explaining ecotoxic effects of nanoparticles in the natural environment.
TL;DR: It is recommended that fullerene nanomaterial not be spread deliberately in the environment and that their ecotoxicology be further clarified.
Abstract: Nanotechnology should produce numerous new materials in the coming years. Because of the novel design of nanomaterials with new physicochemical characteristics, their potential adverse impact on the environment and human health must be addressed. In the present study, agglomerates of pristine C60 fullerenes (50 nm to μm-size) were applied to soil at 0, 5, 25, and 50 mg/kg dry soil to assess their effect on the soil microbiota by measuring total respiration; biomass, number, and diversity of bacteria; and total number and diversity of protozoans during 14 d. Respiration and microbial biomass were unaffected by the fullerenes at any time, whereas the number of fast-growing bacteria was decreased by three- to fourfold just after incorporation of the nanomaterial. Protozoans seemed not to be very sensitive to C60, because their number decreased only slightly in the beginning of the experiment. With polymerase chain reaction and denaturing gradient gel electrophoresis analysis of eubacteria and kinetoplastids from the soil, however, a difference between the fullerene treatments and nonamended controls was demonstrated. The fullerenes did not induce more than 20 to 30% of relative dissimilarity (with both bacteria and protozoans) between treatments, but this effect was persistent throughout the experiment. It therefore is recommended that fullerene nanomaterial not be spread deliberately in the environment and that their ecotoxicology be further clarified.
TL;DR: Two-generation fish toxicity tests showed that parental exposure to both compounds affected the performance of offspring, and more research is required to determine potential consequences of long-term exposure to these compounds in aquatic ecosystems.
Abstract: Because of their global distribution, persistence, and tendency to bioaccumulate, concerns about perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) are growing. We determined the toxicity of PFOS and PFOA in several freshwater organisms, including two cladocerans, Daphnia magna and Moina macrocopa, and the teleost Oryzias latipes. In general, PFOS is approximately 10 times more toxic than PFOA in these organisms. In M. macrocopa, the median lethal concentration (LC50) was 17.95 mg/L for PFOS and 199.51 mg/L for PFOA. Moina macrocopa exhibited greater sensitivity than D. magna to both perfluorinated compounds in both acute and chronic exposures. In the 48-h acute toxicity test, M. macrocopa was approximately two times more sensitive than D. magna. In the 7-d chronic toxicity test, M. macrocopa showed significant reproductive changes at 0.31 mg/L for PFOS, which was approximately seven times lower than the effect concentrations observed over the 21-d exposure in D. magna. Two-generation fish toxicity tests showed that parental exposure to both compounds affected the performance of offspring. Unexposed progeny-generation (F1) fish exhibited elevated mortality and histopathological changes that were correlated with exposure in the parental generation (F0). Continuous exposure from F0 through F1 generations increased the extent of adverse effects. Considering the persistent nature of PFOS and PFOA, more research is required to determine potential consequences of long-term exposure to these compounds in aquatic ecosystems.
TL;DR: It can be concluded that effluent from all types of mill processes are capable of affecting fish reproduction and that any improvements could not be attributed to a specific process modification (because mills normally performed multiple modifications simultaneously).
Abstract: For the last 20 years, studies conducted in North America, Scandinavia, and New Zealand have shown that pulp and paper mill effluents affect fish reproduction. Despite the level of effort applied, few leads are available regarding the factors responsible. Effluents affect reproduction in multiple fish species, as evidenced by decreased gonad size, decreased circulating and gonadal production of reproductive steroids, altered expression of secondary sex characteristics, and decreased egg production. Several studies also have shown that effluent constituents are capable of accumulating in fish and binding to sex steroid receptors/binding proteins. Studies aimed at isolating biologically active substances within the pulping and papermaking process have provided clues about their source, and work has progressed in identifying opportunities for in-mill treatment technologies. Following comparisons of manufacturing processes and fish responses before and after process changes, it can be concluded that effluent from all types of mill processes are capable of affecting fish reproduction and that any improvements could not be attributed to a specific process modification (because mills normally performed multiple modifications simultaneously). Improved reproductive performance in fish generally was associated with reduced use of molecular chlorine, improved condensate handling, and liquor spill control. Effluent biotreatment has been effective in reducing some effects, but biotreated effluents also have shown no difference or an exacerbation of effects. The role of biotreatment in relation to effects on fish reproduction remains unclear and needs to be resolved.
TL;DR: Results indicate that coatings present on nanocry crystals provide protection from metal toxicity during laboratory exposures but that the transfer of core metals from intact nanocrystals may occur at levels well above toxic threshold values, indicating the potential exposure of higher trophic levels.
Abstract: Innovative research and diagnostic techniques for biological testing have advanced during recent years because of the development of semiconductor nanocrystals. Although these commercially available, fluorescent nanocrystals have a protective organic coating, the inner core contains cadmium and selenium. Because these metals have the potential for detrimental environmental effects, concerns have been raised over our lack of understanding about the environmental fate of these products. U.S. Environmental Protection Agency test protocol and fluorescence microscopy were used to determine the fate and effect of quantum dots (QDs; Qdot® 545 ITK™ Carboxyl Quantum Dots [Fisher Scientific, Fisher part Q21391MP; Invitrogen Molecular Probes, Eugene, OR, USA]) using standard aquatic test organisms. No lethality was measured following 48-h exposure of Ceriodaphnia dubia to QD suspensions as high as 110 ppb, but the 96-h median lethal concentration to Pseudokirchneriella subcapitata was measured at 37.1 ppb. Transfer of QDs from dosed algae to C. dubia was verified with fluorescence microscopy. These results indicate that coatings present on nanocrystals provide protection from metal toxicity during laboratory exposures but that the transfer of core metals from intact nanocrystals may occur at levels well above toxic threshold values, indicating the potential exposure of higher trophic levels. Studies regarding the fate and effects of nanoparticles can be incorporated into models for predictive toxicology of these emerging contaminants.
TL;DR: In this article, the Henderson-Hasselbalch equation was applied to calculate dissociation of organic electrolytes to soil, and regression equations were developed to predict separately for the neutral and ionic molecule species the distribution coefficient (Ka) normalized to organic carbon (Koc) from log Kow and pKa.
Abstract: The sorption of organic electrolytes to soil was investigated. A dataset consisting of 164 electrolytes, composed of 93 acids, 65 bases, and six amphoters, was collected from literature and databases. The partition coefficient log Kow of the neutral molecule and the dissociation constant pKa were calculated by the software ACD/Labs. The Henderson-Hasselbalch equation was applied to calculate dissociation. Regressions were developed to predict separately for the neutral and the ionic molecule species the distribution coefficient (Ka) normalized to organic carbon (Koc) from log Kow and pKa. The log Koc of strong acids (pKa 7.5), probably due to electrical interactions. Nonetheless, their log Koc was highly correlated to log Kow. For bases, a nonlinear regression was developed, too. The new regression equations are applicable in the whole pKa range of acids, bases, and amphoters and are useful in particular for relatively strong bases and amphoters, for which no predictive methods specifically have been developed so far.
TL;DR: Biotransformation rate constants calculated by the proposed method are compared with other published estimates for 31 chemicals that range in octanol–water partition coefficients from approximately 101 to 108 and represent over four orders of magnitude in biotransformation potential.
Abstract: A method is proposed for estimating metabolic biotransformation rate constants for nonionic organic chemicals from measured laboratory bioconcentration and dietary bioaccumulation data in fish. Data have been selected based on a quality review to reduce uncertainty in the measured values. A kinetic mass balance model is used to estimate rates of chemical uptake and elimination. Biotransformation rate constants are essentially calculated as the difference between two quantities, a measured bioconcentration factor or elimination rate constant, and a model-derived bioconcentration factor or elimination rate constant estimated assuming no biotransformation. Model parameterization exploits key empirical data when they are available and assumes default values when study specific data are unavailable. Uncertainty analyses provide screening level assessments for confidence in the biotransformation rate constant estimates. The uncertainty analyses include the range for 95% of the predicted values and 95% confidence intervals for the calculated biotransformation values. Case studies are provided to illustrate the calculation and uncertainty methods. Biotransformation rate constants calculated by the proposed method are compared with other published estimates for 31 chemicals that range in octanol-water partition coefficients from approximately 10(1) to 10(8) and represent over four orders of magnitude in biotransformation potential. The comparison of previously published values with those calculated by the proposed method shows general agreement with 82% of the estimated values falling within a factor of three.
TL;DR: In this paper, the authors investigated the association of a C60 water suspension (nC6) with natural organic matter, present as a soil constituent or dissolved in the water column, and its effect on the antibacterial activity of nC60.
Abstract: The present study investigated the association of a C60 water suspension (nC6) with natural organic matter, present as a soil constituent or dissolved in the water column, and its effect on the antibacterial activity of nC60. Sorption of nC60 to soil reduced its bioavailability and antibacterial activity, and the sorption capacity strongly depended on the organic content of the soil. Adsorption of aquatic dissolved humic substances onto nC60 and possible subsequent reactions also were found to eliminate nC60 toxicity at humic acid concentrations as low as 0.05 mg/L. These findings indicate that natural organic matter in the environment can mitigate significantly the potential impacts of nC60 on microbial activities that are important to ecosystem health.
TL;DR: Examination of the toxicity of four PPCPs to midge Chironomus tentans and the freshwater amphipod Hyalella azteca in 10-d waterborne exposures concludes that potential risks exist toward benthic invertebrates for theoxicity of TCS and CBZ and that further investigations of these compounds are required to characterize more completely the risks tobenthic organisms.
Abstract: Despite concerns about potential risks associated with the presence of pharmaceuticals and personal care products (PPCPs) in the environment, few toxicological data address the effects of these compounds. In aquatic systems, which often represent the final repository for PPCPs, increasing toxicological information regarding aquatic biota is improving our capacity to assess potential risks. However, responses of key biota, such as benthic invertebrates, have not been investigated as widely. In the present study, we examined the toxicity of four PPCPs—the lipid regulator atorvastatin (ATO), the antiepileptic drug carbamazepine (CBZ), the synthetic hormone 17-ethinylestradiol (EE 2), and the antimicrobial triclosan (TCS)—to the midge Chironomus tentans and the freshwater amphipod Hyalella azteca in 10-d waterborne exposures. The toxicity of the four compounds varied between 0.20 and 47.3 mg/L (median lethal concentration), with a relative toxicity ranking of TCS EE 2 ATO CBZ. Hyalella azteca was more sensitive than C. tentans to these compounds. The toxicity data were used in a hazard quotient approach to evaluate the risk posed by the four PPCPs to benthic invertebrates and other aquatic organisms. For each compound, a hazard quotient was calculated by dividing the lowest toxicity value by the highest exposure value found in the literature, to which an uncertainty factor was applied. With hazard quotients of 3.55 to 11.5, we conclude that potential risks exist toward benthic invertebrates for the toxicity of TCS and CBZ and that further investigations of these compounds are required to characterize more completely the risks to benthic organisms. In contrast, our data also indicate that considering the low concentrations currently detected in the environment, ATO and EE 2 pose negligible risks to benthic invertebrates.
TL;DR: The present findings imply that the oxidative stress induced by long-term exposure could be the main mechanism of the toxicity of nC60/aq to juvenile carp.
Abstract: The rapid growth of nanotechnology is stimulating research concerning the potential environmental impacts of manufactured nanomaterials. The present study summarizes, to our knowledge, the first examination regarding the potential effects of chronic exposure (32 d) of aquatic organisms (juvenile carp [Carassius auratus]) to sublethal concentrations (0.04-1.0 mg/L) of fullerene aggregates (nC60/aq; i.e., C60 suspended in water after long-term stirring) with average diameters of approximately 349 and/or 1,394 nm. The results demonstrated that the antioxidant enzymes superoxide dismutase and catalase were induced significantly in the gills and liver of C. auratus exposed to nC60/aq for 32 d, whereas a nonenzymatic antioxidant, glutathione, decreased in all tested tissues. In addition, lipid peroxidation (LPO) levels decreased in most cases, especially in the gills and brain, but exposure to 1.0 mg/L of nC60/aq led to a significant (p < 0.01) increase in the LPO level in the liver. This increase in LPO level in combination with the observed oxidative stress suggested that the liver might be the target of or most susceptible organ to nC60/ aq exposure. Furthermore, the body weight and total length of juvenile carp exposed to 1.0 mg/L of nC60/aq for 32 d decreased significantly (p < 0.05), indicating that nC60/aq had an inhibitory effect on fish growth. The present findings imply that the oxidative stress induced by long-term exposure could be the main mechanism of the toxicity of nC60/aq to juvenile carp. This important work contributes to a better understanding of the potential health effects of exposure to manufactured nanomaterials on species in aquatic ecosystems.
TL;DR: Modest correlations are found, suggesting some consistency in biotransformation capabilities between fish and microorganisms, in a database of measured laboratory bioconcentration factors and total elimination rate constants for fish.
Abstract: Biotransformation is a key process that can mitigate the bioaccumulation potential of organic substances and is an important parameter for exposure assessments. A recently published method for estimating whole-body in vivo metabolic biotransformation rate constants (kM) is applied to a database of measured laboratory bioconcentration factors and total elimination rate constants for fish. The method uses a kinetic mass balance model to estimate rates of chemical uptake and elimination when measured values are not reported. More than 5400 measurements for more than 1000 organic chemicals were critically reviewed to compile a database of 1535 kM estimates for 702 organic chemicals. Biotransformation rates range over six orders of magnitude across a diverse domain of chemical classes and structures. Screening-level uncertainty analyses provide guidance for the selection and interpretation of kM values. In general, variation in kM estimates from different routes of exposure (water vs diet) and between fish species is approximately equal to the calculation uncertainty in kM values. Examples are presented of structure-biotransformation relationships. Biotransformation rate estimates in the database are compared with estimates of biodegradation rates from existing quantitative structure-activity relationship models. Modest correlations are found, suggesting some consistency in biotransformation capabilities between fish and microorganisms. Additional analyses to further explore possible quantitative structure-biotransformation relationships for estimating kM from chemical structure are encouraged, and recommendations for improving the database are provided.
TL;DR: It is suggested that blood is an excellent, nonlethal predictor of HG concentrations in internal tissues but that feathers are relatively poor indicators of Hg concentrations inInternal tissues.
Abstract: Despite a large body of research concerning mercury (Hg) in birds, no single tissue has been used consistently to assess Hg exposure, and this has hampered comparisons across studies. We evaluated the relationships of Hg concentrations among tissues in four species of waterbirds (American avocets [Recurvirostra americana], black-necked stilts [Himantopus mexicanus], Caspian terns [Hydroprogne caspia; formerly Sterna caspia], and Forster's terns [Sterna forsteri]) and across three life stages (prebreeding adults, breeding adults, and chicks) in San Francisco Bay, California, USA. Across species and life stages, Hg concentrations (least square mean +/- standard error) were highest in head feathers (6.45 +/- 0.31 microg/g dry wt) and breast feathers (5.76 +/- 0.28 microg/g dry wt), followed by kidney (4.54 +/- 0.22 microg/g dry wt), liver (4.43 +/- 0.21 microg/g dry wt), blood (3.10 +/- 0.15 microg/g dry wt), and muscle (1.67 +/- 0.08 microg/g dry wt). Relative Hg distribution among tissues, however, differed by species and life stage. Mercury concentrations were highly correlated among internal tissues (r2 > or = 0.89). Conversely, the relationships between Hg in feathers and internal tissues were substantially weaker (r2 < or = 0.42). Regression slopes sometimes differed among species and life stages, indicating that care must be used when predicting Hg concentrations in one tissue based on those in another. However, we found good agreement between predictions made using a general tissue-prediction equation and more specific equations developed for each species and life stage. Finally, our results suggest that blood is an excellent, nonlethal predictor of Hg concentrations in internal tissues but that feathers are relatively poor indicators of Hg concentrations in internal tissues.
TL;DR: The effects on growth observed in the present study are important because of the unique dipteran life cycle involving pupation and emergence events, and dipterans may be important for estimating risk and understanding effects of phenylpyrazole‐class insecticides on benthic macroinvertebrate communities.
Abstract: Pyrethroids and fipronil insecticides partition to sediment and organic matter in aquatic systems and may pose a risk to organisms that use these matrices. It has been suggested that bioavailability of sediment-sorbed pesticides is reduced, but data on toxicity of sediment-associated pesticides for pyrethroids and fipronil are limited. In the current study, 10-d sediment exposures were conducted with larval Chironomus tentans for bifenthrin, lambda-cyhalothrin, permethrin, fipronil, fipronil-sulfide, and fipronil- sulfone, the last two being common fipronil metabolites. Sublethal endpoints included immobilization, instantaneous growth rate (IGR), body condition index, and growth estimated by ash-free dry mass (AFDM). Pyrethroid lethal concentrations to 50% of the population (LC50s) were 6.2, 2.8, and 24.5 g/g of organic carbon (OC) for bifenthrin, lambda-cyhalothrin, and permethrin, respectively; with the former two lower than previously published estimates. Fipronil, fipronil-sulfide, and fipronil-sulfone LC50 values were 0.13, 0.16, and 0.12 g/g of OC, respectively. Ratios of LC50s to sublethal endpoints (immobilization, IGR, and AFDM) ranged from 0.90 to 9.03. The effects on growth observed in the present study are important because of the unique dipteran life cycle involving pupation and emergence events. Growth inhibition would likely lead to ecological impacts similar to mortality (no emergence and thus not reproductively viable) but at concentrations up to 4.3 times lower than the LC50 for some compounds. In addition, C. tentans was highly sensitive to fipronil and metabolites, suggesting that dipterans may be important for estimating risk and understanding effects of phenylpyrazole-class insecticides on benthic macroinvertebrate communities. Keywords—Chironomus tentans Fipronil Pyrethroids Sediment toxicity Sublethal responses
TL;DR: To quantify the effects that soil physicochemical properties have on various ecotoxicological endpoints, including phytotoxicity, 14 agricultural soils from Australia with differing soil properties were spiked with copper (Cu) and zinc (Zn) salts and used to conduct plant growth inhibition tests using wheat in pot trials.
Abstract: Interest is mounting in developing and utilizing soil-specific soil quality guidelines. This requires quantifying the effects that soil physicochemical properties have on various ecotoxicological endpoints, including phytotoxicity. To this end, 14 agricultural soils from Australia with differing soil properties were spiked with copper (Cu) and zinc (Zn) salts and used to conduct 21-d plant growth inhibition tests using wheat (Triticum aestivum L.) in pot trials. The toxicity of Cu and Zn was similar with 10% effect concentration (EC10) values ranging from 110 to 945 and from 235 to 965 mg/kg, respectively, while the corresponding median effect concentration (EC50) values ranged from 240 to 1,405 and 470 to 1,745 mg/kg, respectively. Copper toxicity values (EC10, EC20, and EC50) were best modeled by the logarithm of cation exchange capacity (CEC) and either soil pH or electrical conductivity. Zinc EC50 and EC20 values were best modeled using the logarithm of CEC, while the EC10 data were best modeled using soil pH and the logarithm of organic carbon. These models generally estimated toxicity within a factor of two of the measured values.
TL;DR: The results show that surface water ecosystems in unconfined aquifer settings are susceptible to contamination by estrogenic and other biologically active OWCs through recharge from aquifers contaminated by residential septic systems.
Abstract: Increasing residential development in watershed recharge areas increases the likelihood of groundwater and surface water contamination by wastewater effluent, particularly where on-site sewage treatment is employed. This effluent contains a range of compounds including those that have been demonstrated to mimic or interfere with the function of natural hormones in aquatic organisms and humans. To explore whether groundwater contaminated by discharge from on-site septic systems affects water quality in surface water ecosystems, we measured steroidal hormones, pharmaceuticals, and other organic wastewater compounds (OWCs) in water collected from six aquifer-fed ponds in areas of higher and lower residential density on Cape Cod (Massachusetts, USA). We detected both a greater number and higher concentrations of OWCs in samples collected from ponds located in higher residential density areas. Most often detected were the steroidal hormones androstenedione, estrone, and progesterone and the pharmaceuticals carbamazepine, pentoxifylline, sulfamethoxazole, and trimethoprim. Of particular concern, estrogenic hormones were present at concentrations approaching those that induce physiological responses in fish. While a number of papers have reported on surface water contamination by OWCs from wastewater treatment plants, our results show that surface water ecosystems in unconfined aquifer settings are susceptible to contamination by estrogenic and other biologically active OWCs through recharge from aquifers contaminated by residential septic systems.
TL;DR: In this article, a feasible method has been optimized to simultaneously determine multiclass antibiotic residues, including sulfonamides, fluoroquinolones, trimethoprim, and chloramphenicol in urban riverine water and wastewater by off-line solid phase extraction and high-performance liquid chromatography coupled with a diode-array ultraviolet detector and a fluorescence detector.
Abstract: A feasible method has been optimized to simultaneously determine multiclass antibiotic residues, including sulfonamides, fluoroquinolones, trimethoprim, and chloramphenicol in urban riverine water and wastewater by off-line solid phase extraction and high-performance liquid chromatography coupled with a diode-array ultraviolet detector and a fluorescence detector. Internal standard and standard addition methods were used in combination to identify and quantify these antibiotics to compensate for the matrix interference. The method quantification limits (MQLs) were determined to be 0.035 to 0.100 microg/L and 0.100 to 0.300 microg/L for the riverine water and wastewater, respectively. Recoveries of the investigated antibiotics ranged from 63 to 126%. Sulfamethoxazole was the most frequently detected antibiotic residue in Guangzhou section of the Major Pearl River, South China, with a maximum level of 0.510 microg/L. Fluoroquinolone antibiotics were relatively less detected with a maximum level of 0.459 microg/L. The maximum concentration of sulfamethoxazole reached 5.597 microg/L in the raw wastewater from a large-scale sewage treatment plant in Guangzhou city. Around 30% of sulfamethoxazole might survive the primary clarification and biotreatment processes in the sewage treatment plant. None of the investigated antibiotics have been found above MQLs in the final effluent after chlorine disinfection.
TL;DR: This is the first publication on the application of extraction methods for nC60 from ultrapure and tap waters and determination of detection limits by LC/MS.
Abstract: The growing usage of nanomaterials is causing emerging concern regarding their environmental behavior in aquatic environments. A major need is the capability to detect and quantify nanomaterials in complex water matrices. Carbon60 fullerene is of special interest because of the widespread application of nanocarbon technology. The present study focuses on how to separate and concentrate fullerenes from water containing salts and organic matter and then quantify their concentrations using liquid chromatography coupled with mass spectrometry (LC/MS). The stable aqueous C60 aggregates (nC60) prepared in the present study were approximately 60 to 70 nm in diameter and had an ultraviolet (UV) extinction coefficient of 0.0263 L/mg-cm at 347 nm, which equated to a UV detection limit of 0.4 mg/L based upon an absorbance of 0.01 cm−1. Ultraviolet analysis is not applicable to use in waters containing salts or organics (e.g., tap water) because of their interferences and potential to aggregate nC60 The LS/MS analysis detected C60 as single fullerene rather than aggregates. Three techniques were developed to separate and concentrate nC60 from ultrapure and tap water into toluene to facilitate LC/MS determination: Evaporation of sample to dryness; extraction using 20% NaCl into toluene; and solid-phase extraction. The first two methods had limitations for use in complex water matrices, but aqueous nC60 concentration as low as 300 ng/L in water were quantified using solid-phase extraction (SPE) separation method. This is the first publication on the application of extraction methods for nC60 from ultrapure and tap waters and determination of detection limits by LC/MS.
TL;DR: Findings demonstrate that nC 60 transport and retention in water-saturated sand is strongly dependent on electrolyte conditions and that release of deposited nC60 requires substantial changes in surface charge, consistent with retention in a primary energy minimum.
Abstract: The potential toxicity of nanoscale particles has received considerable attention, but the fate of engineered nanomaterials in the environment has been studied only under a limited set of conditions. In the present study, batch and column experiments were performed to assess the aggregation and transport of nanoscale fullerene (nC60) particles in water-saturated quartz sands as a function of electrolyte concentration and species. As the electrolyte concentration increased from 1 to 100 mM, the change in nC60 particle diameter was minimal in the presence of NaCl but increased by more than sevenfold in the presence of CaCl2. The latter effect was attributed to the agglomeration of individual nC60 particles, consistent with a net attractive force between particles and suppression of the electrical double layer. At low ionic strength (3.05 mM), nC60 particles were readily transported through 40- to 50-mesh quartz sand, appearing in the column effluent after introducing less than 1.5 pore volumes of nC60 suspension, with approximately 30% and less than 10% of the injected mass retained in the presence of CaCl2 or NaCl, respectively. At higher ionic strength (30.05 mM) and in finer Ottawa sand (100-140 mesh), greater than 95% of the introduced nC60 particles were retained in the column regardless of the electrolyte species. Approximately 50% of the deposited nC60 particles were recovered from 100- to 140-mesh Ottawa sand after sequential introduction of deionized water adjusted the pH to 10 and 12. These findings demonstrate that nC60 transport and retention in water-saturated sand is strongly dependent on electrolyte conditions and that release of deposited nC60 requires substantial changes in surface charge, consistent with retention in a primary energy minimum.