Acute toxicity of selected organic pollutants to saltwater (mysid Siriella armata) and freshwater (cladoceran Daphnia magna) ecotoxicological models.

The acute toxicity of three organophosphate pesticides (diazinon, chlorpyrifos, pirimiphos-methyl) two chlorinated biocides (endosulfan, pentachlorophenol) and a nonsteroidal anti-inflammatory drug (diclofenac) was tested on <24 h neonates of saltwater mysidacea (Siriella armata) in laboratory acute toxicity test. The 50 and 10 % lethal effective concentrations (LC(50) and LC(10)), NOEC and LOEC values were calculated. The three organophosphate pesticides showed an apparently biphasic dose-response profile, supporting that its mechanism of action in crustaceans differ from other organic compounds. The biphasic pattern of response was confirmed using the common aquatic ecotoxicological model Daphnia magna. According to the 96-h LC(50) values for S. armata, the ranking of toxicity was chlorpyrifos (0.13 µg/L) < pirimiphos-methyl (1.3 µg/L) < endosulfan (3.2 µg/L) < diazinon (4.03 µg/L) < pentachlorophenol (262.2 µg/L) < diclofenac (2919 µg/L). In general, mysids resulted at least one order of magnitude more sensitive than model daphnia, which stresses the need for using marine species for the derivation of seawater quality standards.

Communication: reduced density matrices in molecular systems: grand-canonical electron states.

Grand-canonical like descriptions of many electron atomic and molecular open systems which are characterized by a non-integer number of electrons are presented. Their associated reduced density matrices (RDMs) are obtained by introducing the contracting mapping for this type of distributions. It is shown that there is loss of information when connecting RDMs of different order by partial contractions. The energy convexity property of these systems simplifies the description. Consequently, this formulation opens the possibility to a new look for chemical descriptors such as chemical potential and reactivity among others. Examples are presented to discuss the theoretical aspects of this work.

Microplastics increase the toxicity of mercury, chlorpyrifos and fluoranthene to mussel and sea urchin embryos.

The objective of this study was to determine whether and to what extent microplastics (MPs) enhance the toxicity of pollutants as well as whether pollutant-loaded MPs act as relevant vectors of chemical pollutants. With this aim, the toxicity for mussel and sea urchin embryos of: 1) three dissolved pollutants (Pol): chlorpyrifos (CPF), fluoranthene (FLT) and mercury (Hg); 2) their mixture with Microplastics (MP + Pol); and 3) pollutant-loaded MPs (MPPol), was assessed. Analyses of CPF, FLT and Hg were also performed to evaluate the transfer among dissolved and particulate phases. In general, the 'MP + Pol' treatments were more toxic as 48-h EC50 (µg/L) than the 'Pol' treatments for sea urchin or mussel. The 48-h and 120-h EC50s (µg/L) for sea urchin showed little variation for CPF and MP + CPF, and no clear pattern was found for FLT and MP + FLT. The performed chemical analysis in the MPPol tests indicated that desorption was the main route to explain the observed toxicity of Hg and a relevant route for CPF and FLT. This study contributes to improve the knowledge about the interactions between MPs and chemical pollutants, which is fundamental for a more realistic ecological risk assessment in aquatic ecosystems.

Note: Energy convexity and density matrices in molecular systems.

A novel appropriate definition for the density matrix for an interacting Coulombic driven atomic or molecular system with non-integer number of particles is given. Our approach leads to a direct derivation of the proposal reported by Perdew et al. [Phys. Rev. Lett. 49, 1691 (1982)] and points out its suitability and perspective advances.

Prospective ecological risk assessment of sediment resuspension in an estuary.

This study assesses potential ecological risk of resuspended sediment in the water column during the construction of a viaduct in the estuary of the Ulla river (Galicia, NW Iberian Peninsula), a shellfish production area. Chemical analyses and toxicity bioassays with elutriates were performed with sediments from the area where the three pillars of the viaduct will be located (CT1, CT2 and CT3) and a reference sediment (A2). Acute toxicity of the elutriate was evaluated in five species of three trophic levels (Isochrysis galbana, Paracentrotus lividus, Mytilus galloprovincialis, Venerupis pullastra and Siriella armata). The sediments of the pillars showed moderate levels of contamination by trace elements (Cu, Cr). Clam and sea urchin embryo-larval toxicity tests showed slightly higher sensitivity than mussel embryo tests, and toxicity was not detected for phytoplankton and mysid bioassays. The predicted no-effect environmental concentration (PNEC) was calculated from the arithmetic mean of the lowest calculated EC(50)s for each sampling site. The predicted environmental concentration (PEC) was estimated from a simple dilution model and the PEC/PNEC ratio was calculated according to different scenarios of resuspension. Negligible ecological risk in the water column is expected during construction of the pillars.

Ecological risk assessment of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) in marine environment using Isochrysis galbana, Paracentrotus lividus, Siriella armata and Psetta maxima.

Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) are anthropogenic substances classified as persistent bioaccumulative compounds and are found in various environmental compartments throughout the world, from industrialized regions to remote zones far from areas of production. In this study, we assessed the effects of PFOA and PFOS on early life stages of marine test species belonging to three different trophic levels: one microalga (Isochrysis galbana), a primary consumer (Paracentrotus lividus) and two secondary consumers (Siriella armata and Psetta maxima). Acute EC(50) values for PFOS were 0.11 mg L(-1) in P. maxima, 6.9 mg L(-1) in S. armata, 20 mg L(-1) in P. lividus and 37.5 mg L(-1) in I. galbana. In the case of PFOA, the toxicity was lower but the ranking was the same; 11.9 mg L(-1) in P. maxima, 15.5 mg L(-1) in S. armata, 110 mg L(-1) in P. lividus and 163.6 mg L(-1) in I. galbana. The Predicted No Effect Concentration (PNEC) for PFOS and PFOA in marine water derived from these acute toxicity values are 1.1 µg L(-1) for PFOS and 119 µg L(-1) for PFOA. This study established a baseline dataset of toxicity of PFOS and PFOA on saltwater organisms. The data obtained suggest that PFOA pose a minor risk to these organisms through direct exposure. In the perspective of risk assessment, early life stage (ELS) endpoints provide rapid, cost-effective and ecologically relevant information, and links should be sought between these short-term tests and effects of long-term exposures in more realistic scenarios.

Post-incident monitoring to evaluate environmental damage from shipping incidents: chemical and biological assessments.

Oil and chemical spills in the marine environment are an issue of growing concern. Oil exploration and exploitation is moving from the continental shelf to deeper waters, and to northern latitudes where the risk of an oil spill is potentially greater and may affect pristine ecosystems. Moreover, a growing number of chemical products are transported by sea and maritime incidents of hazardous and noxious substances (HNS) are expected to increase. Consequently, it seems timely to review all of the experience gained from past spills to be able to cope with appropriate response and mitigation strategies to combat future incidents. Accordingly, this overview is focused on the dissemination of the most successful approaches to both detect and assess accidental releases using chemical as well as biological approaches for spills of either oil or HNS in the marine environment. Aerial surveillance, sampling techniques for water, suspended particles, sediments and biota are reviewed. Early warning bioassays and biomarkers to assess spills are also presented. Finally, research needs and gaps in knowledge are discussed.

Linking biochemical and individual-level effects of chlorpyrifos, triphenyl phosphate, and bisphenol A on sea urchin (Paracentrotus lividus) larvae.

The effects of three relevant organic pollutants: chlorpyrifos (CPF), a widely used insecticide, triphenyl phosphate (TPHP), employed as flame retardant and as plastic additive, and bisphenol A (BPA), used primarily as plastic additive, on sea urchin (Paracentrotus lividus) larvae, were investigated. Experiments consisted of exposing sea urchin fertilized eggs throughout their development to the 4-arm pluteus larval stage. The antioxidant enzymes glutathione reductase (GR) and catalase (CAT), the phase II detoxification enzyme glutathione S-transferase (GST), and the neurotransmitter catabolism enzyme acetylcholinesterase (AChE) were assessed in combination with responses at the individual level (larval growth). CPF was the most toxic compound with 10 and 50% effective concentrations (EC10 and EC50) values of 60 and 279 µg/l (0.17 and 0.80 µM), followed by TPHP with EC10 and EC50 values of 224 and 1213 µg/l (0.68 and 3.7 µM), and by BPA with EC10 and EC50 values of 885 and 1549 µg/l (3.9 and 6.8 µM). The toxicity of the three compounds was attributed to oxidative stress, to the modulation of the AChE response, and/or to the reduction of the detoxification efficacy. Increasing trends in CAT activity were observed for BPA and, to a lower extent, for CPF. GR activity showed a bell-shaped response in larvae exposed to CPF, whereas BPA caused an increasing trend in GR. GST also displayed a bell-shaped response to CPF exposure and a decreasing trend was observed for TPHP. An inhibition pattern in AChE activity was observed at increasing BPA concentrations. A potential role of the GST in the metabolism of CPF was proposed, but not for TPHP or BPA, and a significant increase of AChE activity associated with oxidative stress was observed in TPHP-exposed larvae. Among the biochemical responses, the GR activity was found to be a reliable biomarker of exposure for sea urchin early-life stages, providing a first sign of damage. These results show that the integration of responses at the biochemical level with fitness-related responses (e.g., growth) may help to improve knowledge about the impact of toxic substances on marine ecosystems.

Evaluation of toxic effects of several carboxylic acids on bacterial growth by toxicodynamic modelling.

BACKGROUND: Effects of organic acids on microbial fermentation are commonly tested in investigations about metabolic behaviour of bacteria. However, they typically provide only descriptive information without modelling the influence of acid concentrations on bacterial kinetics. RESULTS: We developed and applied a mathematical model (secondary model) to capture the toxicological effects of those chemicals on kinetic parameters that define the growth of bacteria in batch cultures. Thus, dose-response kinetics were performed with different bacteria (Leuconostoc mesenteroides, Carnobacterium pisicola, Escherichia coli, Bacillus subtilis and Listonella anguillarum) exposed at increasing concentrations of individual carboxylic acids (formic, acetic, propionic, butyric and lactic). In all bioassays the acids affected the maximum bacterial load (Xm) and the maximum growth rate (vm) but only in specific cases the lag phase (λ) was modified. Significance of the parameters was always high and in all fermentations the toxicodynamic equation was statistically consistent and had good predictability. The differences between D and L-lactic acid effects were significant for the growth of E. coli, L. mesenteroides and C. piscicola. In addition, a global parameter (EC50,τ) was used to compare toxic effects and provided a realistic characterization of antimicrobial agents using a single value. CONCLUSIONS: The effect of several organic acids on the growth of different bacteria was accurately studied and perfectly characterized by a bivariate equation which combines the basis of dose-response theory with microbial growth kinetics (secondary model). The toxicity of carboxylic acids was lower with the increase of the molecular weight of these chemicals.

Effects of three heavy metals on the bacteria growth kinetics: a bivariate model for toxicological assessment.

The effects of three heavy metals (Co, Ni and Cd) on the growth kinetics of five bacterial strains with different characteristics (Pseudomonas sp., Phaeobacter sp. strain 27-4, Listonella anguillarum, Carnobacterium piscicola and Leuconostoc mesenteroides subsp. lysis) were studied in a batch system. A bivariate model, function of time and dose, is proposed to describe simultaneously all the kinetic profiles obtained by incubating a microorganism at increasing concentrations of individual metals. This model combines the logistic equation for describing growth, with a modification of the cumulative Weibull's function for describing the dose-dependent variations of growth parameters. The comprehensive model thus obtained--which minimizes the effects of the experimental error--was statistically significant in all the studied cases, and it raises doubts about toxicological evaluations that are based on a single growth parameter, especially if it is not obtained from a kinetic equation. In lactic acid bacteria cultures (C. piscicola and L. mesenteroides), Cd induced remarkable differences in yield and time course of characteristic metabolites. A global parameter is defined (ED(50,τ): dose of toxic chemical that reduces the biomass of a culture by 50% compared to that produced by the control at the time corresponding to its semi maximum biomass) that allows comparing toxic effects on growth kinetics using a single value.

Acute toxicity of a shoreline cleaner, CytoSol, mixed with oil and ecological risk assessment of its use on the Galician Coast.

The application of embryo-larval bioassay with the purple sea urchin Paracentrotus lividus and the mussel Mytilus galloprovincialis at 48 hours, and with neonates of the mysid Siriella armata at 96 hours, was used to evaluate the acute toxicities of the following preparations: (1) the shoreline cleaning agent CytoSol; (2) the water-accommodated fraction of CytoSol plus a light crude oil; and (3) the runoff from a pilot-scale treatment with CytoSol of a rocky coastal substrate impregnated with residues from the Prestige oil spill (which occurred on November 19, 2002). The mussel was the most sensitive organism to CytoSol and runoff effects (EC(50) = 8.0 microL/L and 64.3 mL/L, respectively), and the mysid was the least sensitive to the runoff (EC(50) > 200 mL/L). The predicted no-effect environmental concentration (PNEC) was calculated from the no observed-effect concentration of the species most sensitive to the runoff. The predicted environmental concentration (PEC) was estimated from a simple and reasonable dilution model, and the PEC/PNEC ratio was calculated according to the area treated and the values of the variables considered in the model. Implications for the management of the treatment operations are discussed.

Extended imposex monitoring in N Atlantic Spain confirms punctual attainment of European environmental objectives for TBT.

Legislation in the European Union (EU) aimed at reaching by 2015 a Good Ecological Status in regard to tributyltin (TBT, the biocide used in traditional antifouling paints). With a view to check such an achievement in N Atlantic Spain, baseline monitoring of gastropod imposex (the recommended assessment tool) was extended up to that date. In Galicia (the Western part of the study area) the use of the rock snail Nucella lapillus since 1996 had shown this environmental objective to be met as soon as 2009, but new surveys reveal no further improvement thereafter. As for the Eastern Cantabrian coast, imposex levels in the mud snail Nassarius reticulatus progressively declined from 2006 to 2015, when records finally complied with expectations. Both data sets are confronted and discussed in relation to the diverse environmental factors that may be determining the distribution of gastropods in these regions.

Toxicity of seabird guano to sea urchin embryos and interaction with Cu and Pb.

Guano is an important source of marine-derived nutrients to seabird nesting areas. Seabirds usually present high levels of metals and other contaminants because the bioaccumulation processes and biotic depositions can increase the concentration of pollutants in the receiving environments. The objectives of this study were to investigate: the toxicity of seabird guano and the joint toxicity of guano, Cu and Pb by using the sea urchin embryo-larval bioassay. In a first experiment, aqueous extracts of guano were prepared at two loading rates (0.462 and 1.952 g L(-1)) and toxicity to sea-urchin embryos was tested. Toxicity was low and not dependent of the load of guano used (EC50 0.42 ± 0.03 g L(-1)). Trace metal concentrations were also low either in guano or in aqueous extracts of guano and the toxicity of extracts were apparently related to dissolved organic matter. In a second experiment, the toxicity of Cu-Pb mixtures in artificial seawater and in extracts of guano (at two loadings: 0.015 and 0.073 g L(-1)), was tested. According to individual fittings, Cu added to extracts of guano showed less toxicity than when dissolved in artificial seawater. The response surfaces obtained for mixtures of Cu and Pb in artificial seawater, and in 0.015 g L(-1) and 0.073 g L(-1) of guano, were better described by Independent Action model adapted to describe antagonism, than by the other proposed models. This implied accepting that EC50 for Cu and Pb increased with the load of guano and with a greater interaction for Cu than for Pb.

Inhibition of selected bacterial growth by three hydrocarbons: mathematical evaluation of toxicity using a toxicodynamic equation.

The individual toxicity of different hydrocarbons (naphthalene, cyclododecane and aniline) on the growth of selected bacteria (Pseudomonas sp., Phaeobacter sp. and Leuconostoc mesenteroides) was studied by means of a toxicodynamic model combination of two sigmoid equations (logistic and Weibull). All the toxicological effects on growth parameters and kinetic properties were characterized and the global toxicity of such chemicals was evaluated. It was observed that two kinetic parameters (maximum growth and maximum growth rate) were in almost all cases influenced by the hydrocarbons studied. Aniline was less toxic than cyclododecane and naphthalene. The presented approach is a reasonable starting point for understanding and modeling complete and real assessment of chemical toxic effects on bacterial growths. The values of EC50,τ could be used for a most efficient comparison of the individual toxicity of chemicals.

Toxicity of spill-treating agents and oil to sea urchin embryos.

The aim of this study was to assess the joint toxicity of a Maya crude oil and four spill-treating agents (STAs) (CytoSol, Finasol OSR51, Agma OSD569 and OD4000). The acute toxicity of the binary mixtures of the water accommodated fractions (WAFs) obtained independently for the oil and each STA was assessed. The toxicity of the chemically enhanced WAF (CEWAF) of oil and Finasol OSR51 at several dispersant to oil ratios (1:2, 1:10 and 1:100) was also evaluated. The toxicity (EC50) obtained for the WAFs of the STAs was: CytoSol (15.1 mL/L)

Toxicity of four spill-treating agents on bacterial growth and sea urchin embryogenesis.

The toxicity of spill-treating agents (STAs) is a topic that needs to be assessed prior to their potential application in environmental disasters. The aim of the present work was to study the effects of four commercial STAs (CytoSol, Finasol OSR 51, Agma OSD 569 and OD4000) on the growth of marine (Phaeobacter sp., Pseudomonas sp.) and terrestrial (Leuconostoc mesenteroides) bacteria, and sea urchin (Paracentrotus lividus) embryolarval development. In general, STA did not inhibit significantly the biomass production of the tested marine bacteria. Finasol OSR 51 and OD4000 clearly inhibited the growth of L. mesenteroides and an accurate description of the kinetics was provided by a proposed bivariate equation. For this species, a global parameter (EC50,τ) was defined to summarize the set of growth kinetics. Using this parameter Finasol OSR 51 was found to be less toxic (754µL L(-1)) than OD4000 (129µL L(-1)). For the sea urchin embryo assay, the ranking of toxicity as EC50 (µL L(-1)) was Agma OSD 569 (34.0)

Effects of simulated weathering on the toxicity of selected crude oils and their components to sea urchin embryos.

Artificial weathering of Angolan crude and a Heavy Fuel Oil (HFO) was performed by evaporation and photooxidation. The aliphatic, aromatic, polar and asphaltene fractions of the fresh and weathered oils were isolated. The toxicity of the water accommodated fraction or an oil/fraction dissolved in DMSO was assessed using the sea urchin embryo test. Photooxidation was observed to decrease the aromatics content and increase polar compounds. A slight reduction in the toxicity of Angolan crude was observed following weathering for the water-accommodated fraction and the extract in DMSO, but no effect was seen for the Heavy Fuel Oil. For aliphatic compounds, the toxicity decreased in the order fresh>evaporated>photooxidated for both Angolan crude and HFO. Weathering slightly increased the toxicity of the aromatic and polar fractions of the oil. The aromatic fractions were responsible for most of the toxicity and the polar compounds were the second most important toxic components, despite having less or similar abundance than the aliphatic fraction. The toxic contribution of the aromatic compounds was higher for the HFO than for the Angolan crude. A decrease in the toxicity of Angolan crude following weathering correlated with a reduction in the toxicity of the aliphatic fraction.

Effects of spill-treating agents on growth kinetics of marine microalgae.

The effects of four spill-treating agents (STAs) (CytoSol, Finasol(®) OSR 51, Agma OSD 569 and OD4000) on the growth kinetics of three marine microalgae (Isochrysis galbana, Chaetoceros gracilis, Phaeodactylum tricornutum) were studied. Chlorophyll a concentration and optical density at 700 nm were assessed to describe the logistic growth of algae in batch cultures. The optical density data were initially analyzed as described for standard algal growth inhibition tests and subsequently modelled by a bivariate model, as a function of time and dose, to assess the toxic effects on growth parameters. Increasing trends in EC50 and EC10 values with time were found with the standard approach. In 8 of the 11 tests, the lag phase (λ) or the time required to achieve half the maximum biomass (τ) was significantly dependent on the STA concentration. A global parameter (EC50,τ) was calculated to summarize the effects of STAs on growth parameters in the bivariate model. The ranking of sensitivity as EC50,τ values was I. galbana>C. gracilis>P. tricornutum. For all species tested, the least toxic agent was Agma OSD 569, followed by CytoSol. The mathematical model allowed successful ecotoxicological evaluation of chemicals on microalgal growth.

Toxicity of binary mixtures of oil fractions to sea urchin embryos.

The assumption of additive toxicity for oil compounds is related to a narcotic mode of action. However, the joint toxicity of oil fractions has not been fully investigated. A fractionation of Maya crude oil into aliphatics, aromatics and polars was performed, fractions were dissolved in dimethyl sulfoxide (DMSO) and subsequently toxicity of single fractions and binary mixtures was assessed using the sea urchin embryo test. The descriptive ability of Concentration Addition (CA), Independent Action (IA) and modifications of both models for describing the joint toxicity of mixtures has also been evaluated. The hydrocarbon content extractable with dichloromethane of the fractions dissolved in DMSO was: 12.0 ± 1.8 mg mL(-1), 39.0 ± 0.5 mg mL(-1) and 20.5 ± 2.5 mg mL(-1) for aliphatics, aromatics and polars, respectively. The toxicity of the extracts in DMSO of the fractions as EC50 (µLL(-1)) was: aliphatics (165.8-242.3)

Dose-response modelling with two agents: application to the bioassay of oil and shoreline cleaning agents.

Single and joint effects of hydrocarbons and a shoreline cleaning agent (SCA) were studied by measuring the inhibition of the larval growth of sea urchin. Different dosage methods of hydrophobic compounds were compared. The results obtained in the evaluation of CytoSol toxicity revealed that the method of variable dilution of water accommodated fraction (WAF) led to the more conservative toxicological approach. Regarding to Libyan oil, the use of DMSO as carrier allowed us the evaluation of its potential toxicity in comparison with the limitations imposed to the use of WAF method. A reparametrised form of the Weibull equation was slightly modified to be useful for dose-response analysis. This was the basis for modelling single sigmoid responses, which were used to simulate biphasic profiles with addition of effects and to describe both the concentration addition (CA) and independent action (IA) hypotheses. In all cases, its descriptive ability was graphically and statistically satisfactory. The IA model was the best option to explain the combined experimental responses obtained.