Effects of carboxylic acids on nC60 aggregate formation

The discovery that negatively charged aggregates of C₆₀ fullerene (nC₆₀) are stable in water has raised concerns regarding the potential environmental and health effects of these aggregates. In this work, we show that nC₆₀ aggregates produced by extended mixing in the presence of environmentally relevant carboxylic acids (acetic acid, tartaric acid, citric acid) have surface charge and morphologic properties that differ from those produced by extended mixing in water alone. In general, aggregates formed in the presence of these acids have a more negative surface charge and are more homogeneous than those produced in water alone. Carboxylic acid identity, solution pH, and sodium ion concentration, which are all intricately coupled, play an important role in setting the measured surface charge. Comparisons between particle sizes determined by analysis of TEM images and those obtained by dynamic light scattering (DLS) indicate that DLS results require careful evaluation when used to describe nC₆₀ aggregates.     

Novel application of the CORAL software to model cytotoxicity of metal oxide nanoparticles to bacteria Escherichia coli

Convenient to apply and available on the Internet software CORAL (http://www.insilico.eu/CORAL) has been used to build up quantitative structure-activity relationships (QSAR) for prediction of cytotoxicity of metal oxide nanoparticles to bacteria Escherichia coli (minus logarithm of concentration for 50% effect pEC50). In this study six random splits of the data into the training and test set were examined. It has been shown that the CORAL provides a reliable tool that could be used to build up a QSAR of the pEC50.     

Susceptibility of epigeic earthworm Eisenia fetida to agricultural application of six insecticides

Ecotoxicological risks of agricultural application of six insecticides to soil organisms were evaluated by acute toxicity tests under laboratory condition following OECD guidelines using the epigeic earthworm Eisenia fetida as the test organism. The organochlorine insecticide endosulfan (LC₅₀ - 0.002 mg kg⁻¹) and the carbamate insecticides aldicarb (LC₅₀ - 9.42 mg kg⁻¹) and carbaryl (LC₅₀ - 14.81 mg kg⁻¹) were found ecologically most dangerous because LC₅₀ values of these insecticides were lower than the respective recommended agricultural dose (RAD). Although E. fetida was found highly susceptible to the pyrethroid insecticide cypermethrin (LC₅₀ - 0.054 mg kg⁻¹), the value was higher than its RAD. The organophosphate insecticides chlorpyrifos (LC₅₀ - 28.58 mg kg⁻¹), and monocrotophos (LC₅₀ - 39.75 mg kg⁻¹) were found less toxic and ecologically safe because the LC₅₀ values were much higher than their respective RAD.     

Toxicity of lead on Ceriodaphnia dubia in the presence of nano-CeO(2) and nano-TiO(2)

Although engineered nanoparticles (NPs) could negatively impact environmental organisms, the synergistic effect of NPs and other toxic substances, which could be more significant than that of NP alone, have seldom been examined. The effect of two common NPs, nano-CeO₂ and nano-TiO₂, on the toxicity of Pb was evaluated using Ceriodaphnia dubia (C. dubia) as the model organism. Standard EPA procedures were followed in the toxicity evaluation. The toxicity of bare NPs (without Pb) was first evaluated and safe doses (levels without causing lethal effect) of NPs were used in the synergistic studies. It was found that the overall toxicity of Pb in the system containing NPs was greater than that of Pb alone, as indicted by the reduced median lethal concentration (LC₅₀) of soluble Pb. The sorption of Pb onto the NP, and the uptake of NPs in the gastrointestinal tract of C. dubia were validated. Therefore, the uptake of Pb-loaded NPs increased the exposure of C. dubia to Pb, resulting in the enhanced toxicity. Reducing the solution pH could shift Pb speciation and enhance the overall toxicity of Pb, with or without the presence of NPs.     

Isonychia spp. and macroinvertebrate community responses to stressors in streams utilizing the benthic in situ toxicity identification evaluation (BiTIE) method

Exposures of caged organisms in situ have proven to be a useful way to improve exposure realism and link to stressor effects in aquatic assessments of hazard or risk. A novel cage system, the benthic in situ toxicity identification evaluation (BiTIE), was developed for benthic macroinvertebrates (surrogate species, resident populations and communities) to separate low and high flow effects, and major chemical classes of stressors in streams. Three resin types were used to separate the chemical stressors in the streams Honey Creek and Little Beavercreek, Ohio, USA: Dowex Optipore (non-polar organics), zeolite (ammonia), and polywool (control). Isonychia spp. sensitivity was compared to Chironomus tentans, and no significant differences were found (p>0.05). Isonychia spp. growth (length) showed a stressor response in the zeolite treatments, and community testing revealed improved metric responses in the Dowex treatments. The BiTIE chamber system demonstrated stressor-response relationships using sublethal and multimetric endpoints.     

Growth and photosynthetic responses to copper in wild grapevine

The present study evaluates the tolerance and accumulation potential of Vitis vinifera ssp. sylvestris under moderate and high external Cu levels. A greenhouse experiment was conducted in order to investigate the effects of a range of external Cu concentrations (0–23 mmol L⁻¹) on growth and photosynthetic performance by measuring gas exchange, chlorophyll fluorescence parameters and photosynthetic pigments. We also measured the total copper, nitrogen, phosphorus, sulphur, calcium, magnesium, iron, potassium and sodium concentrations in the plant tissues. All the experimental plants survived even with external Cu concentrations as high as 23 mmol L⁻¹ (1500 mg Cu L⁻¹), although the excess of metal resulted in a biomass reduction of 35%. The effects of Cu on growth were linked to a reduction in net photosynthesis, which may be related to the effect of the high concentration of the metal on photosynthetic electron transport. V. vinifera ssp. sylvestris survived with leaf Cu concentrations as high as 80 mg kg⁻¹ DW and growth parameters were unaffected by leaf tissue concentrations of 35 mg Cu kg⁻¹ DW. The results of our study indicate that plants of V. vinifera ssp. sylvestris from the studied population are more tolerant to Cu than the commercial varieties of grapevine that have been studied in the literature, and could constitute a basis for the genetic improvement of Cu tolerance in grapevine.     

Gene expression responses of paper birch (Betula papyrifera) to elevated CO2 and O3 during leaf maturation and senescence

Gene expression responses of paper birch (Betula papyrifera) leaves to elevated concentrations of CO₂ and O₃ were studied with microarray analyses from three time points during the summer of 2004 at Aspen FACE. Microarray data were analyzed with clustering techniques, self-organizing maps, K-means clustering and Sammon's mappings, to detect similar gene expression patterns within sampling times and treatments. Most of the alterations in gene expression were caused by O₃, alone or in combination with CO₂. O₃ induced defensive reactions to oxidative stress and earlier leaf senescence, seen as decreased expression of photosynthesis- and carbon fixation-related genes, and increased expression of senescence-associated genes. The effects of elevated CO₂ reflected surplus of carbon that was directed to synthesis of secondary compounds. The combined CO₂ + O₃ treatment resulted in differential gene expression than with individual gas treatments or in changes similar to O₃ treatment, indicating that CO₂ cannot totally alleviate the harmful effects of O₃.     

Integration of biological responses from a suite of bioassays for the Venice Lagoon (Italy) through sediment toxicity index - Part A: Development and comparison of two methodological approaches

Marine and coastal quality assessment, based on test batteries involving a wide array of endpoints, organisms and test matrices, needs for setting up toxicity indices that integrate multiple toxicological measures for decision-making processes and that classify the continuous toxicity response into discrete categories according to the European Water Framework Directive.Two toxicity indices were developed for the lagoon environment such as the Venice Lagoon. Stepwise procedure included: the construction of a database that identified test-matrix pairs (indicators); the selection of a minimum number of ecotoxicological indicators, called toxicological core metrics (CMs-tox) on the basis of specific criteria; the development of toxicity scores for each CM-tox; the integration of the CMs-tox into two indices, the Toxicity Effect Index (TEI), based on the transformation of Toxic Unit (TU) data that were integrated as logarithmic sum, and the Weighted Average Toxicity Index (WATI), starting from toxicity classes integrated as weighted mean. Results from the indices are compared; advantages and drawbacks of both approaches are discussed.     

Evaluation of UV/TiO(2) and UV/ZnO photocatalytic systems coupled to a biological process for the treatment of bleaching pulp mill effluent

This paper presents an exploratory study of pulp mill bleaching effluent treatment by a biological-photocatalytic coupled system. A fungus, Trametes pubescens, immobilized on polyurethane foam was used to inoculate the biological pre-treatment system. The pretreated effluent was then exposed to a photocatalytic treatment in which two catalysts (TiO₂ and ZnO) and two supports (aluminum foil and Luffa cylindrica) were tested. Catalyst characterization was carried out by means of X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). Information about crystalline structure, chemical composition, morphology, homogeneity and distribution on the support surface area was obtained. The overall biological-photocatalytic coupled system achieved degradation of 96% of initial total organic carbon (TOC), 97% of 2-chlorophenol (2-CP), 90% of 2,4-dichlorophenol (2,4-CP) and 99% of 2,4,6-trichlorophenol (2,4,6-TCP). This approach of synergistic coupling of T. pubescens and a semiconductor photocatalyst appears to be a viable alternative for the treatment of these non-biodegradable effluents.     

Effects of chronic elevated ozone exposure on gas exchange responses of adult beech trees (Fagus sylvatica) as related to the within-canopy light gradient

The effects of elevated O₃ on photosynthetic properties in adult beech trees (Fagus sylvatica) were investigated in relation to leaf mass per area as a measure of the gradually changing, within-canopy light availability. Leaves under elevated O₃ showed decreased stomatal conductance at unchanged carboxylation capacity of Rubisco, which was consistent with enhanced δ¹³C of leaf organic matter, regardless of the light environment during growth. In parallel, increased energy demand for O₃ detoxification and repair was suggested under elevated O₃ owing to enhanced dark respiration. Only in shade-grown leaves, light-limited photosynthesis was reduced under elevated O₃, this effect being accompanied by lowered F_v/F_m. These results suggest that chronic O₃ exposure primarily caused stomatal closure to adult beech trees in the field regardless of the within-canopy light gradient. However, light limitation apparently raised the O₃ sensitivity of photosynthesis and accelerated senescence in shade leaves.     

Cytotoxicity assessment of four pharmaceutical compounds on the zebra mussel (Dreissena polymorpha) haemocytes, gill and digestive gland primary cell cultures

Pharmaceutical compounds are considered the new environmental pollutants but at present few studies have evaluated their ecotoxicity on aquatic invertebrates. This study was aimed to investigate the in vitro cytotoxicity of four common drugs, namely atenolol (ATL), carbamazepine (CBZ), diclofenac (DCF) and gemfibrozil (GEM), on three different cell typologies from the zebra mussel (Dreissena polymorpha): haemocytes, gill and digestive gland cells. Results obtained by the Trypan blue exclusion test revealed that exposure to increasing concentrations (0.001; 0.01; 0.1; 1 and 10 mg L⁻¹) of CBZ, DCF and GEM were able to significantly decrease the viability of each cell type, while the MTT (3(4,5-dimethyl-2thiazholyl)-2,5-diphenyl-2H-tetrazolium bromide) reduction assay highlighted only a slight reduction of mitochondrial activity of gill and digestive gland cells. Overall, DCF was the most cytotoxic drug for zebra mussel cells, followed by GEM, CBZ, while ATL has not a noteworthy toxic potential. Our preliminary results lay the groundwork for further in vitro evaluations, which will allow a better definition of the potential toxicity of these drugs.     

Arsenic release from arsenic-bearing Fe-Mn binary oxide: effects of E(h) condition

Ferric and manganese binary oxide (FMBO) has been successfully used to remediate arsenic-polluted river, but there still lacks sufficient data to evaluate its effects on environments. The release behaviors of iron (Fe), manganese (Mn), and arsenic (As) in different E_h ranges were investigated for As-bearing FMBO sediment after remediating As-polluted DaSha River by FMBO. Under high E_h range (+550 to +400 mV), slight dissolution of Fe and Mn, which corresponded to 12.2% and 25.6%, and less than 5% of As release were observed in 336 h. Under lower E_h range (+50 to −100 mV), elevated extent of the dissolution of Mn and Fe were observed, which corresponded to as high as 61.3% and 70.1%. Under such conditions, the dissolution rate of Mn was higher than that of Fe. Furthermore, from the established relationship of As release and the dissolution of Fe and Mn, the release of As seemed dominated by the dissolution of Fe. X-ray photoelectron spectroscopy (XPS) analysis demonstrated the release of Fe, Mn, As(III), and As(V) after sodium ascorbate-treatment, and the re-adsorption of As(V), as indicated from the increased binding energy of As 3d from 44.78 to 45.83 eV. Surface element composition analysis indicated significant decrease of Mn from 3.22% to 0.54%, slight increase of Fe from 12.45% to 13.67%, and elevated ratio of As from 0.11% to 0.32% accordingly. The main reactions of Fe and Mn dissolution and the pathways of As release under different E_h ranges were also proposed.     

Atmospheric transport of urban-derived NH(x): Evidence from nitrogen concentration and delta(15)N in epilithic mosses at Guiyang, SW China

Nitrogen concentration and δ¹⁵N in 175 epilithic moss samples were investigated along four directions from urban to rural sites in Guiyang, SW China. The spatial variations of moss N concentration and δ¹⁵N revealed that atmospheric N deposition is dominated by NH_x-N from two major sources (urban sewage NH₃ and agricultural NH₃), the deposition of urban-derived NH_x followed a point source pattern characterized by an exponential decline with distance from the urban center, while the agricultural-derived NH_x was shown to be a non-point source. The relationship between moss N concentration and distance (y = 1.5e^−0.13x + 1.26) indicated that the maximum transporting distance of urban-derived NH_x averaged 41 km from the urban center, and it could be determined from the relationship between moss δ¹⁵N and distance [y = 2.54 ln(x) − 12.227] that urban-derived NH_x was proportionally lower than agricultural-derived NH_x in N deposition at sites beyond 17.2 km from the urban center. Consequently, the variation of urban-derived NH_x with distance from the urban center could be modeled as y = 56.272e^−0.116x − 0.481 in the Guiyang area.     

Nano-TiO2 enhances the toxicity of copper in natural water to Daphnia magna

The acute toxicity of engineered nanoparticles (NPs) in aquatic environments at high concentrations has been well-established. This study demonstrates that, at a concentration generally considered to be safe in the environment, nano-TiO₂ remarkably enhanced the toxicity of copper to Daphnia magna by increasing the copper bioaccumulation. Specifically, at 2 mg L⁻¹ nano-TiO₂, the (LC₅₀) of Cu²⁺ concentration observed to kill half the population, decreased from 111 μg L⁻¹ to 42 μg L⁻¹. Correspondingly, the level of metallothionein decreased from 135 μg g⁻¹ wet weight to 99 μg g⁻¹ wet weight at a Cu²⁺ level of 100 μg L⁻¹. The copper was found to be adsorbed onto the nano-TiO₂, and ingested and accumulated in the animals, thereby causing toxic injury. The nano-TiO₂ may compete for free copper ions with sulfhydryl groups, causing the inhibition of the detoxification by metallothioneins.     

Photocatalytic decomposition of crotamiton over aqueous TiO(2) suspensions: determination of intermediates and the reaction pathway

The photocatalytic degradation of crotamiton in aqueous solution using TiO₂ was investigated. To investigate the effect of initial pH, the photodegradation behaviors of three types of pharmaceuticals were compared (crotamiton, clofibric acid, sulfamethoxazole). The degradation rates of crotamiton in the pH range 3-9 were nearly equal, but those of clofibric acid and sulfamethoxazole were affected by pH. At pH > 6.5, TiO₂ particles, clofibric acid and sulfamethoxazole had negative charge, therefore, the repulsive force between TiO₂ particles and anionic pharmaceuticals occurred and a low reaction rate at high pH was observed. The effect of UV intensity and TiO₂ concentration on photodegradation efficiency was also investigated. Linear and logarithmical relationships between UV intensity, TiO₂ concentration and the reaction rate constant were confirmed. Furthermore, the structures of photodegradation intermediates formed concomitantly with the disappearance of crotamiton were estimated. Seven intermediates were characterized by LC/MS/MS analyses, and it was assumed that the photocatalytic degradation of crotamiton was initiated by the attack of electrophilic hydroxyl radicals on aromatic rings and alkyl chains.     

Comparison of solid-phase bioassays and ecoscores to evaluate the toxicity of contaminated soils

Five bioassays (inhibition of lettuce germination and growth, earthworm mortality, inhibition of springtail population growth, avoidance by springtails) were compared, using four coke factory soils contaminated by PAHs and trace elements, before and after biotreatment. For each bioassay, several endpoints were combined in an ‘ecoscore’, a measure of test sensitivity. Ecoscores pooled over all tested bioassays revealed that most organisms were highly sensitive to the concentration of 3-ring PAHs. When four soils were combined, behavioural tests using the springtail Folsomia candida showed higher ecoscores, i.e. they were most sensitive to soil contamination. However, despite overall higher sensitivity of behavioural tests, which could be used for cheap and rapid assessment of soil toxicity, especially at low levels of contamination, some test endpoints were more sensitive than others, and this may differ from a soil to another, pointing to the need for a battery of bioassays when more itemized results are expected.     

Photocatalytic degradation of the fungicide Fenhexamid in aqueous TiO(2) suspensions: identification of intermediates products and reaction pathways

Liquid-chromatography interfaced with time-of-flight mass spectrometry (LC-TOF/MS) was used to separate and characterize the transformation products arising from TiO₂-photocatalytic degradation of the fungicide Fenhexamid (FEX) in aqueous solution under simulated solar irradiation. Prior to identification, irradiated solutions of FEX (10 mg L⁻¹) were concentrated by solid-phase extraction. Assignments of the mass spectra ions were aided by elemental composition calculations, comparison of structural analogues and available literature, and acquired knowledge regarding mass spectrometry of related heterocyclic compounds. The primary transformation intermediates identified were hydroxyl and/or keto-derivatives. Several positional isomers are typically produced as a consequence of the non-selectivity of the OH radical attack. Moreover, products resulted from the cleavage of the amide and NHdichlorophenol bonds were formed. Finally, cyclic - benzo[d]oxazole intermediates are also formed through an intramolecular photocyclization process and cleavage of halogen - carbon bond. In the case of the hydroxy and/or keto-derivatives, the generic fragmentation scheme obtained from the interpretation of the ESI-TOF-MS data cannot be diagnostic to precisely localize the position of the entering substituent on the FEX molecule, and thus to characterize all its possible oxygenated derivatives by assigning a plausible structure with confidence. On the basis of identified products different pathways of photocatalytic degradation of FEX were proposed and discussed.     

Life cycle responses of the midge Chironomus riparius to polycyclic aromatic compound exposure

During acute exposure, polycyclic aromatic compounds (PACs) act mainly by narcosis, but during chronic exposure the same compounds may exert sublethal life cycle effects. The aim of this study was therefore to evaluate the chronic effects of sediment spiked PACs on the emergence of the midge Chironomus riparius. Three isomer pairs were selected, and 28-day LC50 values and 50% emergence times (EMt50) were determined. Concentration-response relationships were observed for phenanthrene, acridine, phenanthridine and acridone. Anthracene and phenanthridone had no effect on total emergence, but did cause a delay in emergence. Calculated porewater LC50 values correlated well with logKow values, suggesting narcosis as mode of action. In contrast, effect concentrations for delay in emergence (EMt50) deviated from narcosis, suggesting a specific mode of action during chronic exposure. It is concluded that emergence is a powerful endpoint to detect life cycle effects of PACs on a key sediment inhabiting invertebrate.     

Effect of gender on physiological and behavioural responses of Gammarus roeseli (Crustacea Amphipoda) to salinity and temperature

The importance of potentially interacting factors in organisms responses to a stress are often ignored or underestimated in ecotoxicology. In laboratory experiments we investigated how gender, temperature and age influence the behaviour and the physiology of the freshwater amphipod Gammarus roeseli under salinity stress. Our results revealed a significant higher sensitivity of females in survival, ventilation and ionoregulation whereas no inter-age differences were reported. Water temperature also exerted a significant effect in survival and ventilation of G. roeseli. Some of those factors appeared to interact significantly. This study provides evidence that gender can affect organisms responses to a stressor and consequently has to be considered while assessing a stress impact. We discussed the potential relationships between biological and behavioural responses.     

Use of sap flow measurements to validate stomatal functions for mature beech (Fagus sylvatica) in view of ozone uptake calculations

For a quantitative estimate of the ozone effect on vegetation reliable models for ozone uptake through the stomata are needed. Because of the analogy of ozone uptake and transpiration it is possible to utilize measurements of water loss such as sap flow for quantification of ozone uptake. This technique was applied in three beech (Fagus sylvatica) stands in Switzerland. A canopy conductance was calculated from sap flow velocity and normalized to values between 0 and 1. It represents mainly stomatal conductance as the boundary layer resistance in forests is usually small. Based on this relative conductance, stomatal functions to describe the dependence on light, temperature, vapour pressure deficit and soil moisture were derived using multivariate nonlinear regression. These functions were validated by comparison with conductance values directly estimated from sap flow. The results corroborate the current flux parameterization for beech used in the DO₃SE model.