Toxicity of two types of silver nanoparticles to aquatic crustaceans Daphnia magna and Thamnocephalus platyurus

Although silver nanoparticles (NPs) are increasingly used in various consumer products and produced in industrial scale, information on harmful effects of nanosilver to environmentally relevant organisms is still scarce. This paper studies the adverse effects of silver NPs to two aquatic crustaceans, Daphnia magna and Thamnocephalus platyurus. For that, silver NPs were synthesized where Ag is covalently attached to poly(vinylpyrrolidone) (PVP). In parallel, the toxicity of collargol (protein-coated nanosilver) and AgNO₃ was analyzed. Both types of silver NPs were highly toxic to both crustaceans: the EC50 values in artificial freshwater were 15–17 ppb for D. magna and 20–27 ppb for T. platyurus. The natural water (five different waters with dissolved organic carbon from 5 to 35 mg C/L were studied) mitigated the toxic effect of studied silver compounds up to 8-fold compared with artificial freshwater. The toxicity of silver NPs in all test media was up to 10-fold lower than that of soluble silver salt, AgNO₃. The pattern of the toxic response of both crustacean species to the silver compounds was almost similar in artificial freshwater and in natural waters. The chronic 21-day toxicity of silver NPs to D. magna in natural water was at the part-per-billion level, and adult mortality was more sensitive toxicity test endpoint than the reproduction (the number of offspring per adult).     

Application of a computational model for Michael addition reactivity in the prediction of toxicity to Tetrahymena pyriformis

A computational model to predict acute aquatic toxicity to the ciliate Tetrahymena pyriformis has been developed. A general prediction of toxicity can be based on three consecutive steps: 1. Identification of a potential reactive mechanism via structural alerts; 2. Confirmation and quantification of (bio)chemical reactivity; 3. Establishing a relationship between calculated reactivity and toxicity. The method described herein uses a combination of a reactive toxicity (RT) model, including computed kinetic rate constants for adduct formation (log k) via a Michael acceptor mechanism of action, and baseline toxicity (BT), modelled by hydrophobicity (octanol-water partition coefficient). The maximum of the RT and BT values defines acute toxicity for a particular compound. The reactive toxicity model is based on site-specific steric and quantum chemical ground state electronic properties. The performance of the model was examined in terms of predicting the toxicity of 106 potential Michael acceptor compounds covering several classes of compounds (aldehydes, ketones, esters, heterocycles). The advantages of the computational method are described. The method allows for a closer and more transparent mechanistic insight into the molecular initiating events of toxicological endpoints.     

Ionic liquids as lubricants or lubrication additives: An ecotoxicity and biodegradability assessment

This paper reports on the (eco)toxicity and biodegradability of ionic liquids considered for application as lubricants or lubrication additives. Ammonium- and pyrrolidinium-based cations combined with methylsulphate, methylsulphonate and/or (CF₃SO₂)₂N⁻ anions were investigated in tests to determine their aquatic toxicity using water fleas Daphnia magna, green algae Selenastrum capricornutum and marine bacteria (Vibrio fischeri). Additional test systems with an isolated enzyme (acetylcholinesterase) and isolated leukaemia cells from rats (IPC-81) were used to assess the biological activity of the ionic liquids. These compounds generally exhibit low acute toxicity and biological activity. Their biodegradability was screened according to OECD test procedures 301 B and 301 F. For choline and methoxy-choline ionic liquids ready biodegradability was observed within 5 or 10 d, respectively. Some of the compounds selected have a considerable potential to contribute to the development of more sustainable products and processes.     

Verification of a source-oriented externally mixed air quality model during a severe photochemical smog episode

The CIT/UCD three-dimensional source-oriented externally mixed air quality model is tested during a severe photochemical smog episode (Los Angeles, 7–9 September 1993) using two different chemical mechanisms that describe the formation of ozone and secondary reaction products. The first chemical mechanism is the secondary organic aerosol mechanism (SOAM) that is based on SAPRC90 with extensions to describe the formation of condensable organic products. The second chemical mechanism is the caltech atmospheric chemistry mechanism (CACM) that is based on SAPRC99 with more detailed treatment of organic oxidation products.The predicted ozone concentrations from the CIT/UCD/SOAM and the CIT/UCD/CACM models agree well with the observations made at most monitoring sites with a mean normalized error of approximately 0.4–0.5. Good agreement is generally found between the predicted and measured NO_x concentrations except during morning rush hours of 6–10 am when NO_x concentrations are under-predicted at most locations. Total VOC concentrations predicted by the two chemical mechanisms agree reasonably well with the observations at three of the four sites where measurements were made. Gas-phase concentrations of phenolic compounds and benzaldehyde predicted by the UCD/CIT/CACM model are higher than the measured concentrations whereas the predicted concentrations of other aromatic compounds approximately agree with the measured values.The fine airborne particulate matter mass concentrations (PM_2.5) predicted by the UCD/CIT/SOAM and UCD/CIT/CACM models are slightly greater than the observed values during evening hours and lower than observed values during morning rush hours. The evening over-predictions are driven by an excess of nitrate, ammonium ion and sulfate. The UCD/CIT/CACM model predicts higher nighttime concentrations of gaseous precursors leading to the formation of particulate nitrate than the UCD/CIT/SOAM model. Elemental carbon and total organic mass are under-predicted by both models during morning rush hour periods. When this latter finding is combined with the NO_x under-predictions that occur at the same time, it suggests a systematic bias in the diesel engine emissions inventory. The mass of particulate total organic carbon is under-predicted by both the UCD/CIT/SOAM and UCD/CIT/CACM models during afternoon hours. Elemental carbon concentrations generally agree with the observations at this time. Both the UCD/CIT/SOAM and UCD/CIT/CACM models predict low concentrations of secondary organic aerosol (SOA) (<3.5 μg m⁻³) indicating that both models could be missing SOA formation pathways. The representation of the aerosol as an internal mixture vs. a source-oriented external mixture did not significantly affect the predicted concentrations during the current study.     

Peroxidase-mediated removal of endocrine disrupting compound mixtures from water

Several classes of oxidative enzymes have shown promise for efficient removal of endocrine disrupting compounds (EDCs) that are resistant to conventional wastewater treatments. Although the kinetics of reactions between individual EDCs and selected oxidative enzymes are well documented in the literature, there has been little investigation of reactions with EDC mixtures. This makes it impossible to predict how enzyme-mediated treatment systems will perform since wastewater effluents generally contain multiple EDCs. This paper reports pseudo-first order rate constants for a model oxidative enzyme, horseradish peroxidase (HRP), during single-substrate (k₁) and mixed-substrate (k_1-MIX) reactions. Measured values are compared with literature values of three Michaelis-Menten parameters: half-saturation constant (K_M), enzyme turnover number (k_CAT), and the ratio k_CAT/K_M. Published reports had suggested that each of these could be correlated with HRP reactivity towards EDCs in mixtures, and empirical results from this study show that K_M can be used to predict the sequence of EDC removal reactions within a particular mixture. We also observed that k_1-MIX values were generally greater than k₁ values and that compounds exhibiting greatest estrogenic toxicities reacted most rapidly in a given mixture. Finally, because K_M may be tedious to measure for every EDC of interest, we have constructed a quantitative structure-activity relationship (QSAR) model to predict these values. This model predicts K_M quite accurately (R² = 89%) based on two molecular characteristics: molecular volume and hydration energy. Its accuracy makes this QSAR a useful tool for predicting which EDCs will be removed most efficiently during enzyme treatment of EDC mixtures.     

Toxicity and metabolism of copper pyrithione and its degradation product, 2,2'-dipyridyldisulfide in a marine polychaete

We conducted acute toxicity tests and sediment toxicity tests for copper pyrithione (CuPT) and a metal pyrithione degradation product, 2,2′-dipyridyldisulfide [(PS)₂], using a marine polychaete Perinereis nuntia. The acute toxicity tests yielded 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 0.06 mg L⁻¹ and 7.9 mg L⁻¹, respectively. Sediment toxicity tests resulted in 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 1.1 mg kg⁻¹ dry wt. and 14 mg kg⁻¹ dry wt., respectively. In addition to mortality, sediment avoidance behavior and decreases in animal growth rate were observed; growth rate was the most susceptible endpoint in the sediment toxicity tests of both toxicants. Thus, we propose lowest observed effect concentrations of 0.3 mg kg⁻¹ dry wt. and 0.2 mg kg⁻¹ dry wt. for CuPT and (PS)₂, respectively, and no observed effect concentrations of 0.1 mg kg⁻¹ dry wt. for both CuPT and (PS)₂. The difference in the toxicity values between CuPT and (PS)₂ observed in the acute toxicity test was greater than the difference in these values in the sediment toxicity test, and we attribute this to (PS)₂ being more hydrophilic than CuPT. In addition to the toxicity tests, we analyzed conjugation activity of several polychaete enzymes to the toxicants and marked activity of palmitoyl coenzyme-A:biocides acyltransferase and UDP-glucuronosyl transferase was observed.     

Toxicity of tire wear particle leachate to the marine macroalga, Ulva lactuca

Tire wear particles filed from the treads of end-of-life vehicle tires have been added to sea water to examine the release of Zn and the toxicity of the resulting leachate and dilutions thereof to the marine macroalga, Ulva lactuca. Zinc release appeared to be diffusion-controlled, with a conditional rate constant of 5.4 μg[L(h)^1/2]⁻¹, and about 1.6% of total Zn was released after 120 h incubation. Exposure to increasing concentrations of leachate resulted in a non-linear reduction in the efficiency of photochemical energy conversion of U. lactuca and, with the exception of the undiluted leachate, increasing accumulation of Zn. Phototoxicity was significantly lower on exposure to equivalent concentrations of Zn added as Zn(NO₃)₂, suggesting that organic components of leachate are largely responsible for the overall toxicity to the alga. Given the ubiquity and abundance of TWP in urban coastal sediments, the generation, biogeochemistry and toxicity of tire leachate in the marine setting merit further attention.     

Comparison of the cytotoxic responses of Escherichia coli (E. coli) AMC 198 to different fullerene suspensions (nC60)

Fullerenes are set to be produced on an industrial scale in anticipation of their wide applications. This calls for research on their environmental and health impacts. This study investigates and compares the cell toxicity of different aqueous fullerene aggregates. Popular C₆₀ dispersal methods were used to prepare four types of nC₆₀ aggregates. These aggregates were tested against the indicator species Escherichia coli (E. coli) AMC 198. With aggregates of around 150 nm in diameter, the THF/nC₆₀ suspension was very toxic and gave rise to a half maximal effective concentration (EC₅₀) of 0.54 mg L⁻¹ in E. coli. By contrast, the Tol/nC₆₀ suspension exhibited a cytoprotective role while the Aqu-N₂/nC₆₀ and Aqu-O₂/nC₆₀ suspensions enhanced the metabolism of E. coli. Although some toxicants, such as THF and THF-peroxide, were introduced into the THF/nC₆₀ suspension during the dispersion, the toxicity of nC₆₀ itself cannot be neglected.     

Fate of bisphenol A during treatment with the litter-decomposing fungi Stropharia rugosoannulata and Stropharia coronilla

Bisphenol A is an endocrine disrupting compound, which is ubiquitous in the environment due to its wide use in plastic and resin production. Seven day old cultures of the litter-decomposing fungus Stropharia coronilla removed the estrogenic activity of bisphenol A (BPA) rapidly and enduringly. Treatment of BPA with purified neutral manganese peroxidase (MnP) from this fungus also resulted in 100% reduction of estrogenic activity, as analyzed using a bioluminescent yeast assay, and in the formation of polymeric compounds. In cultures of Stropharia rugosoannulata, estrogenic activity also quickly disappeared but temporarily re-emerged in the further course of cultivation. LC-MS analysis of the extracted estrogenic culture liquid revealed [M−H]⁻ ions with m/z values of 219 and 235. We hypothesize that these compounds are ring fission products of BPA, which still exhibit one intact hydroxyphenyl group to interact with estrogen receptors displayed by the yeast.     

Hydroxylated polychlorobornanes--synthesis and characterization of new potential toxaphene metabolites

For decades, toxaphene had been used as a major chloropesticide. Degradation of the multicomponent mixture in the environment was mainly reported to be due to anaerobic dechlorination and hydrodechlorination. Little was known about oxidative transformation processes and the potential hydroxylated metabolites were not available as standard compounds. For this reason we synthesized hydroxylated polychlorobornanes by the UV-induced photochlorination of 2-endo-bornyl acetate with sulfuryl chloride followed by hydrolysis of the acetate moiety. The released polychlorinated 2-endo-hydroxybornanes were slightly higher chlorinated the longer the reaction was maintained. After 8 h, the main products were pentachlorinated hydroxybornanes followed by hexa- and heptachlorinated homologues. Traces of octachlorinated hydroxybornanes were also observed. The GC/ECNI-MS spectra of the products were characterized by the molecular ions and the [M-Cl]⁻ fragment ions. The molecular ions of the polychlorinated hydroxybornanes are isobaric with those of polychlorinated biphenyls. E.g. hexachlorohydroxybornanes (C₁₀H₁₂Cl₆O) and hexachlorobiphenyls (C₁₂H₄Cl₆) show the molecular ion at m/z 358. Based on fractionation experiments on silica with the synthesis products it might be possible that OH-CTTs if present in samples will elute into a more polar fraction usually discarded or not collected. Both problems might explain why these compounds have not been more frequently described in the scientific literature.     

Comparing the sensitivity of soil invertebrates to pesticides with that of Eisenia fetida

The sole routine testing of the standard earthworm Eisenia fetida for the terrestrial risk assessment of pesticides has been under much debate since other soil invertebrates may be more sensitive than this standard test species. However, the very low availability of laboratory toxicity data for taxa other than E. fetida has greatly hampered sensitivity comparisons. In the present study, the relative tolerance (T_rel) approach was used to enable comparing toxicity thresholds obtained from the US-EPA ECOTOX database, for main terrestrial taxonomic groups and pesticidal types of action (insecticides, fungicides, herbicides, and other) separately. Analyses confirmed previously reported lower and higher sensitivity of collembolans to fungicides and insecticides, respectively. However, various other discrepancies in susceptibility relative to E. fetida were encountered as indicated by species sensitivity distributions and/or calculated 95% confidence intervals of T_rel values. Arachnids and isopods were found to be more sensitive to insecticides, and nematodes to fungicides, as compared to E. fetida. Implications of study findings for the terrestrial risk assessment of pesticides are discussed.     

Sorption influenced transport of ionizable pharmaceuticals onto a natural sandy aquifer sediment at different pH

The pH-dependent transport of eight selected ionizable pharmaceuticals was investigated by using saturated column experiments. Seventy-eight different breakthrough curves on a natural sandy aquifer material were produced and compared for three different pH levels at otherwise constant conditions. The experimentally obtained K_OC data were compared with calculated K_OC values derived from two different log K_OW-log K_OC correlation approaches. A significant pH-dependence on sorption was observed for all compounds with pK_a in the considered pH range. Strong retardation was measured for several compounds despite their hydrophilic character. Besides an overall underestimation of K_OC, the comparison between calculated and measured values only yields meaningful results for the acidic and neutral compounds. Basic compounds retarded much stronger than expected, particularly at low pH when their cationic species dominated. This is caused by additional ionic interactions, such as cation exchange processes, which are insufficiently considered in the applied K_OC correlations.     

Time-dependent degradation and toxicity of diclofop-methyl in algal suspensions

Background, aim, and scope  As emerging contaminants, transformation products of the pollutants via various environmental processes are rather unknown, and some may predominately contribute to the environmental risks of the parent compounds. Hence, studies on transformation products complement the assessment of the environmental safety of the parent compounds. In this study, degradation experiments and toxicity tests using diclofop-methyl (DM), a widely used herbicide, and selected major transformation products were carried out in algal cultures to assess the time course of DM toxicity and its relevance in the formation of new breakdown products. Methods  The alga Chlorella vulgaris was maintained in the algal growth medium HB IV. The inhibition of algal growth was determined by measuring optical density at 680 nm (OD₆₈₀). Initially, DM and two selected breakdown products were added to the algal cultures, and following degradation experiments analyses were carried out by high performance liquid chromatography. In addition, the possible relationship between DM degradation and toxicity was assessed, based on physico-chemical properties of the compounds and their toxicity. Results  DM was rapidly absorbed onto the surface of the algal cells where it was hydrolyzed to diclofop (DC). Further degradation to 4-(2, 4-dichlorophenoxy) phenol (DP) occurred in the cells. However, only a minor amount of DC was degraded to DP under the same conditions when DC was initially added to the algal culture. When C. vulgaris was exposed to these compounds for 96 h, the determined EC₅₀ showed that DC was about ten times less toxic than DM (EC₅₀ = 0.42 mg/L) and that DP (EC₅₀ = 0.20 mg/L) was the most toxic. Discussion  Due to strong hydrophobicity and rare dissociation, DM has tendency toward absorption as compared to DC. The higher average degradation rates of DC initially treated by DM revealed the damage of the cell membranes caused by the DM and, thus, enhanced movement of DC into the cells. Following occurrence of phenolic breakdown products, DP suggested that DC should be intracellularly degraded to DP, which had a more potent mode of action and a higher acute toxicity. Moreover, the results for EC₅₀ at various intervals were in accordance with degradation processes of the initial compounds, in which rapid formation of DP was attributed to an increasing toxicity of DM. Conclusions  The toxicity of DM in algal suspensions increased with time due to its degradation to DP, which contributed significantly to the determined toxicity. These results indicate that the toxicity of the pesticide probably depends significantly on degradation. It is thus important to consider the time-dependent environmental processes when evaluating the toxicological effects of pesticides for proper risk assessment. Recommendations and perspectives  Increasing transformation products of these contaminants are identified in the environment, although they seem to be unknown in terms of the lacking studies on environmental behavior and ecotoxicity concerning them. Certain breakdown products probably greatly contribute to the apparent toxicity of the parent compounds, which is ascribed to the parent compounds in general studies ignoring the dependence of their toxicity on various transformation pathways. These studies that identify new intermediates and assess their toxicity via the environmental processes will be helpful to distinguish the nature of toxicity of the parent contaminants.     

Ecotoxicity and fungal deterioration of recycled polypropylene/wood composites: Effect of wood content and coupling

Recycled polypropylene (rPP) was recovered from an industrial shredder and composites were prepared with a relatively wide range of wood content and with two coupling agents, a maleated PP (MAPP) and a maleated ethylene-propylene-diene elastomer (MAEPDM). The mechanical properties of the composites showed that the coupling agents change structure only slightly, but interfacial adhesion quite drastically. The durability of the materials was determined by exposing them to a range of fungi and, ecotoxicity was studied on the aquatic organism Vibrio fischeri. The composites generally exhibit low acute toxicity, with values below the levels considered to have direct ecotoxic effect on aquatic ecosystems (<2 toxic units). Their toxicity to V. fischeri depended on the presence of the coupling agents with larger E₅₀ values in 24-h aqueous extracts from composites containing MAPP or MAEPDM in comparison to composites without any coupling agent. Evaluation of resistance against fungal colonization and deterioration proved that wood facilitates fungal colonization. Fungi caused slight mass loss (below 3%) but it was not correlated with substantial deterioration in material properties. MAPP seems to be beneficial in the retention of mechanical properties during fungal attack. rPP/wood composites can be considered non-ecotoxic and quite durable, but the influence of wood content on resistance to fungal attack must be taken into account for materials intended for applications requiring long-term outdoor exposure.     

Toxicity assessment of the maize herbicides S-metolachlor,benoxacor, mesotrione and nicosulfuron,and their corresponding commercial formulations,alone and in mixtures,using the Microtox® test

The Microtox® test, using the prokaryote Vibrio fischeri, was employed to assess the toxicity of the maize herbicides S-metolachlor, benoxacor, mesotrione and nicosulfuron, and their formulated compounds: Dual Gold Safeneur®, Callisto® and Milagro®; alone and in mixtures. For each compound we obtained original IC₅₀ values, with consistent higher toxicities for formulated compounds compared to active ingredients alone. Mixtures of the four herbicides, prepared according to application doses encountered in agriculture, were found to be toxic at a lower concentration than single molecules. Mesotrione and nicosulfuron mixture appeared to be highly toxic to V. fischeri, however, this recommended post-emergence combination for maize crops got its toxicity decreased in formulated compound mixtures, suggesting that chemical interactions could potentially reduce the toxicity. Data comparisons to theoretical models showed a good prediction of mixture toxicity by Concentration Addition concept. Results seemed to exclude any synergistic effects on V. fischeri for the tested herbicide mixtures. Additional work coupling these bioassay data to ecosystemic level studies (aquatic and soil compartments) and data on additives and degradation products toxicity, will help to fill the gap in our knowledge of the environmental impact of these xenobiotics and in the choice of a more sustainable use of pesticides.     

C60 fullerene: a powerful antioxidant or a damaging agent? The importance of an in-depth material characterization prior to toxicity assays

Since the discovery of fullerenes in 1985, these carbon nanospheres have attracted attention regarding their physico/chemical properties. Despite little knowledge about their impact on the environment and human health, the production of fullerenes has already reached an industrial scale. However, the toxicity of C₆₀ is still controversially discussed.The aim of this study was to clarify the biological effects of tetrahydrofuran (THF) suspended C₆₀ fullerene in comparison to water stirred C₆₀ fullerene suspensions. Beyond that, we analyzed the effects on the Crustacea Daphnia magna an indicator for ecotoxicological effects and the human lung epithelial cell line A549 as a simplified model for the respiratory tract.We could demonstrate that water-soluble side products which were formed in THF nC₆₀ suspension were responsible for the observed acute toxic effects, whereas fullerenes themselves had no negative effect regardless of the preparative route on either A549 cell in vitro or D. magna in vivo.     

Sorption and desorption of carbamazepine, naproxen and triclosan in a soil irrigated with raw wastewater: estimation of the sorption parameters by considering the initial mass of the compounds in the soil

The amphipod Hyalella azteca was exposed for 28 d to different combinations of Zn contaminated sediment and food. Sediment exposure (+clean food) resulted in increased Zn body burdens, increased mortality and decreased body mass when the molar concentrations of simultaneously extracted Zn were greater than the molar concentration of Acid Volatile Sulfide (SEM_Zn-AVS > 0), suggesting that dissolved Zn was a dominant route of exposure. No adverse effect was noted in the foodexposure (+clean sediment), suggesting selective feeding or regulation. Combined exposure (sediment + food) significantly increased adverse effects in comparison with sediment exposure, indicating contribution of dietary Zn to toxicity and bioaccumulation. The observed enhanced toxicity also supports the assumption on the presence of an avoidance/selective feeding reaction of the amphipods in the single sediment or food exposures. During 14 d post-exposure in clean medium, the organisms from the same combined exposure history received two feeding regimes, i.e. clean food and Zn spiked food. Elevated Zn bioaccumulation and reduced reproduction were noted in amphipods that were offered Zn spiked food compared to the respective organisms that were fed clean food. This was explained by the failure of avoidance/selective feeding behavior in the absence of an alternative food source (sediment), forcing the amphipods to take up Zn while feeding. Increasing Zn body burdens rejected the assumption that Zn uptake from food was regulated by H. azteca. Our results show that the selective feeding behavior should be accounted for when assessing ecological effects of Zn or other contaminants, especially when contaminated food is a potential exposure route.