Impacts of aqueous extracts of wildfire ashes on aquatic life-stages of Xenopus laevis: Influence of plant coverage.

Wildfires have emerged as a global ecological concern due to their wide-ranging off-site effects. One particular consequence is the adverse impact on aquatic environments, as wildfires are acknowledged as a significant source of aquatic contamination through ash runoffs containing toxic compounds. Yet, amphibian response to this source of contamination remains largely undocumented. This study assessed how ash runoffs from Eucalyptus sp. and Pinus sp. affect early aquatic life-stages of Xenopus laevis. Embryos and tadpoles were exposed, respectively, for 96 h and 14 days to serial concentrations (26.9% - 100%) of aqueous extracts of ashes (AEAs; 10 gL-1) composed of eucalypt (ELS) and pine (PLS) ashes. Mortality and development were monitored, and biometric data (snout-to-vent, tail and total length, and weight) measured. Sub-individual endpoints regarding oxidative stress (catalase-CAT; total glutathione-TG; lipid peroxidation-TBARS), neurotoxicity (acetylcholinesterase-AChE), transformation metabolism (glutathione-S-transferase-GST) and energetic metabolism (carbohydrate, lipid and protein content and O2 consumption), were also measured. The two AEAs induced no significant lethal effects on embryos or tadpoles. However, in general, AEAs caused a developmental delay in both life stages. Effects of AEAs on biometric endpoint were only reported for tadpoles, which showed a decreased body length (snout-to-vent, tail and total) and weight (embryos were not weighed), with PLS exerting higher effect than ELS. As for the sub-individual endpoints, embryos showed mostly no alterations on the activity of the monitored parameters, except for PLS, which reduced embryos' carbohydrate content (at ≥59.2%) and increased O2 consumption (at ≥35.0%). Regarding tadpoles, AEA exposure decreased the activity of CAT and GST (at ≥26.0%) and decreased carbohydrate (at ≥26.0%) and lipid (at ≥45.5%), whereas oxygen consumption increased (at ≥26.0%) only on PLS. Overall, the tested AEAs differentially affected amphibians across life-stages, indicating that plant coverage might affect ash toxicity.

Improving cost-efficiency for MPs density separation by zinc chloride reuse.

The methodology used to extract and quantify microplastics (MPs) in aquatic systems are still not standardized. Salt saturated solutions, such as sodium chloride (NaCl), zinc chloride (ZnCl2) and/or sodium iodide (NaI), are normally added to separate dense plastics from aquatic samples. However, the most effective reagents are also the most expensive (e.g. ZnCl2 and NaI). To decrease this cost, a reuse process of the salt solutions should be applied. The reuse process has been widely investigated for the NaI solution neglecting the ZnCl2. Hence, the aim of this study was to present a simple methodology to reuse the ZnCl2 solution ensuring the efficiency of the product. Results of the present study showed that ZnCl2 solution could be reused at least five times maintaining an efficiency above 95 %. •The ZnCl2 reuse decreases the cost of the methodology.•The efficiency of ZnCl2 solution after five filtrations remains above 95 % (all polymers are detected and recovered).•The use of this salt solution is the most cost-effective methodology to isolate MPs from aquatic samples.

Impacts of plastic products used in daily life on the environment and human health: What is known?

Plastics are indispensable and persistent materials used in daily life that can be fragmented into micro- or nanoplastics. They are long polymer chains mixed with additives that can be toxic when in contact with distinct species. The toxicity can result from polymer matrix, additives, degradation products and adsorbed contaminants. Notwithstanding, there is still an immense gap of information concerning the individual and mixed impacts of plastics. Hence, in this study, we characterize the most common plastic materials widely used in our daily life by its polymer type and compile the environmental and human health hazards of these polymers including the impacts of monomers, additives, degradation products and adsorbed contaminants based on literature review. In summary, polyvinyl chloride is the most toxic polymer type used daily (monomer and additives); additives are more toxic than monomers to wildlife and humans; and the most toxic additives are benzene, phthalates and lead stabilisers.

Environmental benchmarks based on ecotoxicological assessment with planktonic species might not adequately protect benthic assemblages in lotic systems.

Freshwater ecosystems face widespread diffuse and point-source contamination. Species Sensitivity Distributions (SSDs) have been used as a tool to determine chemical concentration benchmarks that represent protective levels for most species in the environment. Here we used a SSD approach to assess on the adequacy of standard planktonic organisms to reflect the response of benthic communities, critically supporting the structure and function of lotic ecosystems. For the purpose, SSDs reflecting non-lethal responses of standard planktonic and selected benthic organisms were built based on EC50 values (collected in the literature or estimated following testing herein) regarding three model contaminants: potassium dichromate (PD), 3,5-dichlorophenol (DCP) and lead chloride (LC). The derived HC5 estimates were discriminatory between chemicals and the uncertainty associated with the estimate was remarkably low. The HC5 estimates with corresponding uncertainty were generally within the same order of magnitude for the three chemicals tested, with better discrimination between chemicals regarding their hazardous potential being achieved for benthic organisms: DCP was clearly less hazardous than PD, but LC tends to be as hazardous as PD and DCP (assuming the confidence interval ranges). Moreover, benthic communities were more sensitive to both DCP and PD, in this later case the HC5 being lower by more than one order of magnitude than that found for planktonic communities; for LC, confidence intervals overlapped, preventing a feasible assumption regarding differential sensitivity of the compared communities. Microphytobenthos was highlighted as the most sensitive group to the three tested chemicals in SSDs covering the benthic compartment, while SSDs with planktonic organisms did not consistently show trends in sensitivity ordering. Overall, our results suggest that protective benchmarks retrieved from SSDs built with the responses of standard planktonic organisms (which are the most commonly used for regulation purposes) do not adequately protect benthic communities.

Sensitivity of freshwater species under single and multigenerational exposure to seawater intrusion.

Salinization of coastal freshwater ecosystems is already occurring in some regions of the world. This phenomenon raises serious concerns on the protection of coastal freshwater ecosystems, since many of them support and shelter a large number of species and are considered hotspots of biodiversity. This work intended to assess the adverse effects that salinization, caused by the intrusion of seawater (SW), may pose to freshwater organisms. In this study, three specific goals were addressed: (i) to assess if sodium chloride (NaCl) may be used as a surrogate of natural SW at early-stages of risk assessment; (ii) to identify the most sensitive freshwater species to salinity NaCl; and (iii) to determine if increased tolerance to salinity may be acquired after multigenerational exposure to low levels of salinization (induced with NaCl). A total of 12 standard monospecific bioassays were carried out by exposing organisms from different taxonomic groups (Cyanobacteria: one species, Tracheophyta: two species, Rotifera: one species, Arthropoda: two species and Mollusca: one species) to a series of concentrations of NaCl (ranging from 0.95 to 22.8 mS cm-1) or dilutions of SW (ranging from 1.70 to 52.3 mS cm-1). In general, NaCl exerted similar or higher toxicity than SW, both at lethal and sublethal levels, suggesting that it may be proposed as a protective surrogate of SW for first tiers of salinization risk assessment. Among all tested species, the cyanobacterium Cylindrospermopsis raciborskii, the daphnid Daphnia longispina and the rotifer Brachionus plicatilis were the most sensitive taxa to salinization (EC50 ≤ 4.38 mS cm-1). Given their position at the basis of the food web, it is suggested that small increments of salinity may be enough to induce structural changes in freshwater communities or induce changes in trophic relations. No clear evidences of increased tolerance after multigenerational exposure to low levels of salinity were found.This article is part of the theme issue 'Salt in freshwaters: causes, ecological consequences and future prospects'.

Spatial and temporal distribution of microplastics in water and sediments of a freshwater system (Antuã River, Portugal).

Microplastics (particles with a size<5mm), one of the most emerging aquatic pollutants, are of particular concern since they can reach high densities and interact with biotic and abiotic environment. The occurrence of microplastics in freshwater systems is less understood than in marine environment. Hence, the present study aims to provide new insights into microplastics abundances and distribution in Antuã River (Portugal) by applying the isolation method of wet peroxide oxidation with addition of zinc chloride to water and sediment samples collected in March and October 2016, in three sampling sites. The abundance of microplastics in water ranged from 5 to 8.3mgm-3 or 58-193itemsm-3 in March and from 5.8-51.7mgm-3 or 71-1265itemsm-3 in October. In sediments, the abundance ranged from 13.5-52.7mgkg-1 or 100-629itemskg-1 in March and from 2.6-71.4mgkg-1 or 18-514itemskg-1 in October. The water and sediment samples with the greatest abundances were from São João da Madeira and Aguincheira, respectively. Spatio-temporal distribution showed different pattern according to methodological approaches, seasonal and hydrodynamic conditions and the proximity to urban/industry areas. Analysis of plastics by Fourier transform infrared spectroscopy underline polyethylene and polypropylene as the most common polymer types identified in this work. The low medium high oxidation ratio was 56:22:22 (%) in March and 61:31:8 (%) in October. Foams and fibers were the most abundant type in São João da Madeira, while fibers and fragments were the most abundant in Aguincheira and Estarreja in water and sediment samples, respectively. This study emphasizes the importance of rivers as carriage systems of microplastics. Further studies should be performed to identify point sources in order to mitigate the microplastics contamination in aquatic systems.

Impacts of climate and land use changes on the water quality of a small Mediterranean catchment with intensive viticulture.

Studies that address the potential effects of climate and land use changes on surface water quality are scarce in the Mediterranean region. In the present work, the impacts of climate and land use changes on nutrient and copper exports from a humid Mediterranean catchment (São Lourenço) were evaluated using the SWAT model. SWAT reproduced reasonably well total nitrogen (TN), phosphorus (TP) and copper (Cu) exports in São Lourenço, providing an adequate baseline scenario as well as a suitable model parameterization for assessing the impacts of climate and land use changes under the A1B and B1 emission scenarios for the end of the 21st century (2071-2100). Land use changes scenarios were generated along the same storylines as climate change scenarios to assess the combined effects of the two stressors. Climate changes itself led to a decline in annual TN and TP exports under both emission scenarios mostly due to a decrease in runoff and erosion induced by a reduction in rainfall, but it hardly affected Cu exports largely due to its strong immobilization in soils. Land use changes per se resulted in an increase in streamflow, but the changes in water quality varied markedly according to the scenarios. A substantial decrease in TN, TP and Cu exports was observed under scenario A1B, due to a reduction in vineyard areas. Under scenario B1, however, TP exports decreased much less while TN exports hardly changed, reflecting differences in the preferential transport pathways of these compounds. Cu exports also remained the same, as no changes occurred in the vineyard areas. The combination of climate and land use change scenarios revealed additive impacts on the exports of all three contaminants, emphasizing the importance of integrated approaches to define adaptive land management practices that can ensure the future sustainability of Mediterranean water resources.

Effects of dietary exposure to herbicide and of the nutritive quality of contaminated food on the reproductive output of Daphnia magna.

Risk assessment of pesticides has been based on direct toxic effects on aquatic organisms. Indirect effects data are taken into account but with limitations, as it is frequently difficult to predict their real impacts in the ecosystems. In this context the main aim of this work was to assess how the exposure to the herbicide pendimethalin (Prowl(®)), under environmentally relevant concentrations, may compromise the nutritional composition of food for a relevant group of primary consumers of freshwater food webs-the daphnids, thus affecting their reproduction performance and subsequently the long-term sustainability of active populations of this grazer. Therefore, Daphnia magna individuals were chronically exposed in a clean medium to a control diet (NCF - i.e., non-contaminated green algae Raphidocelis subcapitata) and to a contaminated diet (CF - i.e., the same monoalgal culture grown in a medium enriched with pendimethalin in a concentration equivalent to the EC20 for growth inhibition of algae), during which reproductive endpoints were assessed. The algae were analysed for protein, carbohydrate and fatty acid content. The chemical composition of R. subcapitata in the CF revealed a slight decrease on total fatty acid levels, with a particular decrease of essential ω9 monounsaturated fatty acids. In contrast, the protein content was high in the CF. D. magna exposed to CF experienced a 16% reduction in reproduction, measured as the total number of offspring produced per female. Additionally, an internal pendimethalin body burden of 4.226µgg(-1) was accumulated by daphnids fed with CF. Hence, although it is difficult to discriminate the contribution of the pesticide (as a toxic agent transferred through the food web) from that of the food with a poor quality-compromised by the same pesticide, there are no doubts that, under environmentally relevant concentrations of pesticides, both pathways may compromise the populations of freshwater grazers in the long term, with consequences in the control of the primary productivity of these systems.

Impacts of climate and land use changes on the hydrological and erosion processes of two contrasting Mediterranean catchments.

The impacts of climate and land use changes on streamflow and sediment export were evaluated for a humid (São Lourenço) and a dry (Guadalupe) Mediterranean catchment, using the SWAT model. SWAT was able to produce viable streamflow and sediment export simulations for both catchments, which provided a baseline for investigating climate and land use changes under the A1B and B1 emission scenarios for 2071-2100. Compared to the baseline scenario (1971-2000), climate change scenarios showed a decrease in annual rainfall for both catchments (humid: -12%; dry: -8%), together with strong increases in rainfall during winter. Land use changes were derived from a socio-economic storyline in which traditional agriculture is replaced by more profitable land uses (i.e. corn and commercial forestry at the humid site; sunflower at the dry site). Climate change projections showed a decrease in streamflow for both catchments, whereas sediment export decreased only for the São Lourenço catchment. Land use changes resulted in an increase in streamflow, but the erosive response differed between catchments. The combination of climate and land use change scenarios led to a reduction in streamflow for both catchments, suggesting a domain of the climatic response. As for sediments, contrasting results were observed for the humid (A1B: -29%; B1: -22%) and dry catchment (A1B: +222%; B1: +5%), which is mainly due to differences in the present-day and forecasted vegetation types. The results highlight the importance of climate-induced land-use change impacts, which could be similar to or more severe than the direct impacts of climate change alone.

Assessing the ecotoxicity of metal nano-oxides with potential for wastewater treatment.

The rapid development of nanotechnology and the increasing use of nanomaterials (NMs) raise concern about their fate and potential effects in the environment, especially for those that could be used for remediation purposes and that will be intentionally released to the environment. Despite the remarkable emerging literature addressing the biological effects of NMs to aquatic organisms, the existing information is still scarce and contradictory. Therefore, aimed at selecting NMs for the treatment of organic and inorganic effluents, we assessed the potential toxicity of NiO (100 and 10-20 nm), Fe2O3 (≈85 × 425 nm), and TiO2 (<25 nm), to a battery of aquatic organisms: Vibrio fischeri, Raphidocelis subcapitata, Lemna minor, Daphnia magna, Brachionus plicatilis, and Artemia salina. Also a mutagenic test was performed with two Salmonella typhimurium strains. Suspensions of each NM, prepared with the different test media, were characterized by dynamic light scattering (DLS) and eletrophoretic light scattering (ELS). For the assays with marine species, no toxicity was observed for all the compounds. In opposite, statistically significant effects were produced on all freshwater species, being D. magna the most sensitive organism. Based on the results of this study, the tested NMs can be classified in a decreasing order of toxicity NiO (100 nm) > NiO (10-20 nm) > TiO2 (<25 nm) > Fe2O3, allowing to infer that apparently Fe2O3 NMs seems to be the one with less risks for receiving aquatic systems.

Potential risk of biochar-amended soil to aquatic systems: an evaluation based on aquatic bioassays.

It is vital to address potential risks to aquatic ecosystems exposed to runoff and leachates from biochar-amended soils, before large scale applications can be considered. So far, there are no established approaches for such an assessment. This study used a battery of bioassays and representative aquatic organisms for assessing the acute toxicity of water-extractable fractions of biochar-amended soil, at reported application rates (80 t ha(-1)). Biochar-amended aqueous soil extracts contained cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), manganese (Mn), zinc (Zn), nickel (Ni), lead (Pb), arsenic (As) and mercury (Hg) (Σmetals 96.3 µg l(-1)) as well as the 16 priority PAHs defined by the U.S. Environmental Protection Agency (Σ16PAHs 106 ng l(-1)) at contents in the range of current EU regulations for surface waters. Nevertheless, acute exposure to soil-biochar (SB) extracts resulted in species-specific effects and dose-response patterns. While the bioluminescent marine bacterium Vibrio fischeri was the most sensitive organism to aqueous SB extracts, there were no effects on the growth of the microalgae Pseudokirchneriella subcapitata. In contrast, up to 20 and 25% mobility impairment was obtained for the invertebrate Daphnia magna upon exposure to 50 and 100% SB extract concentrations (respectively). Results suggest that a battery of rapid and cost-effective aquatic bioassays that account for ecological representation can complement analytical characterization of biochar-amended soils and risk assessment approaches for surface and groundwater protection.

Ecotoxicological effects of ciprofloxacin on freshwater species: data integration and derivation of toxicity thresholds for risk assessment.

Although antibiotics have been increasingly used and detected in natural samples, their ecotoxicological effects on aquatic wildlife are not yet extensively studied. Considering the environmental threat posed by the biological activity of antibiotics it is quite relevant to assess the resulting impact, especially on sub-lethal endpoints. As such, this study evaluated the effects of ciprofloxacin on Pseudokirchneriella subcapitata and Lemna minor growth, on the survival and reproduction of Daphnia magna and on Gambusia holbrooki survival. The risks associated with ciprofloxacin effects on non-target organisms were quantified through the calculation of the PEC/PNEC ratio. Overall, the toxicity values obtained (at the mg L(-1) level) were higher than the environmental concentrations. P. subcapitata and L. minor were more sensitive under short-term exposures than D. magna and G. holbrooki. No acute toxicity was observed for fish. The chronic assay with D. magna evidenced that long term exposures to lower concentrations of this antibiotic induced impairments on its life-history parameters. Such outcome may pre-empt potential damages on the long-term maintenance of natural populations continuously exposed to the input of antibiotics. Indeed, the PEC/PNEC ratios showed that ciprofloxacin represents a risk for the most sensitive aquatic organisms, since the defined threshold of an acceptable risk was considerably surpassed.

A whole sample toxicity assessment to evaluate the sub-lethal toxicity of water and sediment elutriates from a lake exposed to diffuse pollution.

The impact of diffuse pollution in aquatic systems is of great concern due to the difficult to measure and regulate it. As part of an ecological risk assessment (ERA), this study aims to use a whole sample toxicity assessment to evaluate the toxicity of water and sediment from Lake Vela, a lake that has been exposed to diffuse pollution. In this way, standard (algae: Pseudokirchneriella subcapitata; cladoceran: Daphnia magna) and local species (algae: Aphanizomenon flos-aquae; cladoceran: Daphnia longispina) were exposed to surface water, and sediment elutriates were collected seasonally from two sites at Lake Vela: one near the east bank (ES), surrounded by agricultural lands; and the other near the west bank (WS), surrounded by a forest. The results confirmed the seasonal contamination of both environmental compartments by pesticides, including organochlorine pesticides, and the presence of high concentrations of nutrients. Although both sites were contaminated, higher levels of pesticides and nutrients were detected in ES, particularly in the sediments. Bioassays showed that water samples (100% concentration) collected in summer and autumn significantly affected the growth rate of P. subcapitata, which could be attributed to the presence of pesticides. Likewise, they revealed an apparent toxicity of elutriates for P. subcapitata and for both daphnids, in summer and autumn. In fact, although pesticides were not detected in elutriates, high levels of un-ionized ammonia were recorded, which is considered highly toxic to aquatic life. By comparing the several species, P. subcapitata was revealed to be the most sensitive one, followed by the daphnids, and then by A. flos-aquae. Results obtained in this study underlined the importance of whole samples toxicity assessment for characterizing the ecological effects of complex mixtures from diffuse inputs, in the ERA processes.

Short-term effects of Quirlan (chlorfenvinphos) on the behavior and acetylcholinesterase activity of Gambusia holbrooki.

Chlorfenvinphos is a widespread organophosphorous (OP) insecticide and it is a reported hazardous chemical for aquatic nontarget organisms. This study intended to evaluate the effects of sublethal concentrations of Quirlan(R) (commercial formulation of chlorfenvinphos) on several behavioral parameters of the mosquitofish, Gambusia holbrooki. The insecticide showed high toxicity to G. holbrooki by significantly impairing all the behavioral responses (location in the test vessel, activity/excitability, swimming, and feeding), exhibiting a time-dependent pattern. Behavioral EC50s, after a 96-h exposure, ranged from 5.2 to 9.0 microg L(-1). As OP pesticides are acutely neurotoxic, acetylcholinesterase (AChE) activity was also selected for use as a biomarker in this study for the establishment of a relationship with the observed behavior abnormalities. A strong inhibition of AChE was observed in fish exposed to chlorfenvinphos (IC50 = 3.55 microg L(-1)). Behavioral impairment was registered in fish with >40% AChE inhibition levels, while mortality was only observable in fish exhibiting AChE inhibition levels >80%. Additionally, significant correlations were found between behavioral impairment and AChE inhibition, suggesting a mechanistic link. These results show the usefulness of integrating biochemical and individual endpoints in a small-sized model species, and confirm a potential hazard of chlorfenvinphos to nontarget aquatic organisms.