Isabel Lopes

Nanoscale materials and their use in water contaminants removal—a review

Water scarcity is being recognized as a present and future threat to human activity and as a consequence water purification technologies are gaining major attention worldwide. Nanotechnology has many successful applications in different fields but recently its application for water and wastewater treatment has emerged as a fast-developing, promising area. This review highlights the recent advances on the development of nanoscale materials and processes for treatment of surface water, groundwater and industrial wastewater that are contaminated by toxic metals, organic and inorganic compounds, bacteria and viruses. In addition, the toxic potential of engineered nanomaterials for human health and the environment will also be discussed.

Avoidance of copper contamination by field populations of Daphnia longispina

Almost all terrestrial and aquatic assays that are accepted as standardized, or that have been proposed, involve the exposure of confined organisms to toxicants. If avoidance (sensu evasion, displacement) of contaminants occurs in real situations, then bioassays involving forced exposure severely underestimate pernicious effects of contamination. Two main objectives were achieved in this study: To verify the occurrence of avoidance of copper by cladocerans; to determine the association between avoidance and other toxicity endpoints (lethality and feeding depression), and therefore, to ascertain if fully acclimated individuals from a reference field population exhibited a genetically determined avoidance markedly different from those belonging to a historically metal-stressed population. Twelve cloned lineages of the cladoceran Daphnia longispina, collected from two field populations, were selected according to their lethal sensitivity to copper and acclimated to controlled conditions for more than 30 generations. A 1.1-m test chamber with five compartments was built, allowing the establishment of a dissolved toxicant gradient and the free movement of individuals. In the absence of any toxicant, juveniles from each cloned lineage distributed themselves randomly along the test chamber and furthermore, no significant differences were observed between the two replicates, attesting the repeatability of this novel assay. All lineages showed significant avoidance to copper when exposed to a gradient from 3 to 87 microg/L. The most sensitive lineages to lethal levels of copper began avoiding this metal earlier than resistant ones. An intense association was observed between other endpoints and avoidance; furthermore, avoidance was determined to be much more sensitive than lethality. Therefore, avoidance assays should be recommended as a complementary tool in ecological risk assessments and effluent biomonitoring because such assays can provide cost-effective and ecologically relevant information.

Impact of organic and inorganic nanomaterials in the soil microbial community structure

In this study the effect of organic and inorganic nanomaterials (NMs) on the structural diversity of the soil microbial community was investigated by Denaturing Gradient Gel Electrophoresis, after amplification with universal primers for the bacterial region V6-V8 of 16S rDNA. The polymers of carboxylmethyl-cellulose (CMC), of hydrophobically modified CMC (HM-CMC), and hydrophobically modified polyethylglycol (HM-PEG); the vesicles of sodium dodecyl sulphate/didodecyl dimethylammonium bromide (SDS/DDAB) and of monoolein/sodium oleate (Mo/NaO); titanium oxide (TiO(2)), titanium silicon oxide (TiSiO(4)), CdSe/ZnS quantum dots, gold nanorods, and Fe/Co magnetic fluid were the NMs tested. Soil samples were incubated, for a period of 30 days, after being spiked with NM suspensions previously characterized by Dynamic Light Scattering (DLS) or by an ultrahigh-resolution scanning electron microscope (SEM). The analysis of similarities (ANOSIM) of DGGE profiles showed that gold nanorods, TiO(2), CMC, HM-CMC, HM-PEG, and SDS/DDAB have significantly affected the structural diversity of the soil bacterial community.

Toxicity and genotoxicity of organic and inorganic nanoparticles to the bacteria Vibrio fischeri and Salmonella typhimurium

The present work aimed at evaluating the toxicity and genotoxicity of two organic (vesicles composed of sodium dodecyl sulphate/didodecyl dimethylammonium bromide—SDS/DDAB and of monoolein and sodium oelate—Mo/NaO) and four inorganic (titanium oxide—TiO2, silicon titanium—TiSiO4, Lumidot™-CdSe/ZnS, and gold nanorods) nanoparticles (NP), suspended in two aqueous media (Milli Q® water and American Society for Testing and Materials (ASTM) hardwater), to the bacteria Vibrio fischeri (Microtox® test) and Salmonella typhimurium-his− (Ames® test with strains TA98 and TA100). Aiming a better understanding of these biological responses physical and chemical characterization of the studied NP suspensions was carried out. Results denoted a high aggregation state of the NP in the aqueous suspensions, with the exception of SDS/DDAB and Mo/NaO vesicles, and of nanogold suspended in Milli Q water. This higher aggregation was consistent with the low values of zeta potential, revealing the instability of the suspensions. Regarding toxicity data, except for nano TiO2, the tested NP significantly inhibited bioluminescence of V. fischeri. Genotoxic effects were only induced by SDS/DDAB and TiO2 for the strain TA98. A wide range of toxicity responses was observed for the six tested NP, differing by more than 5 orders of magnitude, and suggesting different modes of action of the tested NP.

Avoidance tests with small fish: Determination of the median avoidance concentration and of the lowest‐observed‐effect gradient

The purpose of the present study was to develop sensitive, rapid, and easily quantified avoidance tests for small fish (Danio rerio) in order to provide important ecological information during toxicity assessments. Fish were exposed in three replicate linear flow-through chambers consisting of five compartments. The test system was found to provide a linear contamination gradient, with mean dilutions in each compartment of 90, 70, 50, 30, and 10%. Also, in the absence of a toxic gradient, the fish were uniformly distributed along the five-compartment chambers. Then the apparatus was evaluated by exposing fish to a concentration gradient of copper and a dilution gradient of a field sample contaminated with acid mine drainage (AMD). Avoidance was monitored at 24-h intervals up to 96 h of exposure. The avoidance of copper and AMD by D. rerio was confirmed. The apparatus enabled quantification of median avoidance effect concentrations or dilutions (EC50 or EDil50) and also lowest-observed-effect gradients, which express the minimum toxicant gradient eliciting avoidance, a parameter increasing the ecological relevance of the laboratory avoidance responses. For quantifying avoidance, a 24-h exposure was sufficient, as the 24- to 96-h EC50 and EDil50 values were similar. The avoidance response was easy and rapid to quantify, leading this test to routine use in environmental risk assessment.

Contaminant driven genetic erosion and associated hypotheses on alleles loss, reduced population growth rate and increased susceptibility to future stressors: an essay

Microevolution due to pollution can occur mainly through genetic drift bottlenecks, especially of small sized populations facing intense lethal pulses of contaminants, through mutations, increasing allelic diversity, and through natural selection, with the disappearance of the most sensitive genotypes. This loss of genotypes can lead to serious effects if coupled to specific hypothetical scenarios. These may be categorized as leading, first, to the loss of alleles—the recessive tolerance inheritance hypothesis. Second, leading to a reduction of the population growth rate—the mutational load and fitness costs hypotheses. Third, leading to an increased susceptibility of further genetic erosion both at future inputs of the same contaminant—differential physiological recovery, endpoints (dis)association, and differential phenotypic plasticity hypotheses—and at sequential or simultaneous inputs of other contaminants—the multiple stressors differential tolerance hypothesis. Species in narrowly fluctuating environments (tropics and deep sea) may have a particularly high susceptibility to genetic erosion—the Plus ça change (plus c’est la meme chose) hypothesis. A discussion on the consequences of these hypotheses is what this essay aimed at.

Label-free disposable immunosensor for detection of atrazine

This work reports the construction of a fast, disposable, and label-free immunosensor for the determination of atrazine. The immunosensor is based on a field effect transistor (FET) where a network of single-walled carbon nanotubes (SWCNTs) acts as the conductor channel, constituting carbon nanotubes field effect transistors (CNTFETs). Anti-atrazine antibodies were adsorbed onto the SWCNTs and subsequently the SWCNTs were protected with Tween 20 to prevent the non-specific binding of bacteria or proteins. The principle of the immunoreaction consists in the direct adsorption of atrazine specific antibodies (anti-atrazine) to SWCNTs networks. After exposed to increasing concentrations of atrazine, the CNTFETs could be used as useful label-free platforms to detect atrazine. Under the optimal conditions, a limit of detection as low as 0.001 ng mL(-1) was obtained, which is lower than that of other methods for the atrazine detection, and in a working range between 0.001 and 10 ng mL(-1). The average recoveries obtained for real water samples spiked with atrazine varied from 87.3% to 108.0%. The results show that the constructed sensors display a high sensitivity and could be useful tools for detecting pesticides like atrazine at low concentrations. They could be also applied to the determination of atrazine in environmental aqueous samples, such as seawater and riverine water.

Screening evaluation of the ecotoxicity and genotoxicity of soils contaminated with organic and inorganic nanoparticles: The role of ageing

This study aimed to evaluate the toxicity and genotoxicity of soils, and corresponding elutriates, contaminated with aqueous suspensions of two organic (vesicles of sodium dodecyl sulphate/didodecyl dimethylammonium bromide and of monoolein and sodium oleate) and five inorganic nanoparticles (NPs) (TiO(2), TiSiO(4), CdSe/ZnS quantum dots, Fe/Co magnetic fluid and gold nanorods) to Vibrio fischeri and Salmonella typhimurium (TA98 and TA100 strains). Soil samples were tested 2h and 30 days after contamination. Suspensions of NPs were characterized by Dynamic Light Scattering. Soils were highly toxic to V. fischeri, especially after 2h. After 30 days toxicity was maintained only for soils spiked with suspensions of more stable NPs (zeta potential>30 mV or <-30 mV). Elutriates were particularly toxic after 2h, except for soil spiked with Fe/Co magnetic fluid, suggesting that ageing may have contributed for degrading the organic shell of these NPs, increasing the mobility of core elements and the toxicity of elutriates. TA98 was the most sensitive strain to the mutagenic potential of soil elutriates. Only elutriates from soils spiked with gold nanorods, quantum dots (QDs) and TiSiO(4) induced mutations in both strains of S. typhimurium, suggesting more diversified mechanisms of genotoxicity.

The water-soluble fraction of potentially toxic elements in contaminated soils: relationships between ecotoxicity, solubility and geochemical reactivity.

To better understand the impacts posed by soil contamination to aquatic ecosystems it is crucial to characterise the links between ecotoxicity, chemical availability and geochemical reactivity of potentially toxic elements (PTEs) in soils. We evaluated the adverse effects of water extracts obtained from soils contaminated by chemical industry and mining, using a test battery including organisms from different trophic levels (bacteria, algae and daphnids). These tests provided a quick assessment of the ecotoxicity of soils with respect to possible adverse effects on aquatic organisms although the ecotoxicological responses could be related to the solubility of PTEs only to a limited extent. The analysis of results of bioassays together with the chemical characterisation of water extracts provided additional relevant insight into the role of conductivity, pH, Al, Fe, and Mn of soil extracts on toxicity to organisms. Furthermore, an important conclusion of this study was that the toxicity of extracts to the aquatic organisms could also be related to the soil properties (pH, Org C and Fe(ox)) and to the reactivity of PTEs in soils which in fact control the soluble fraction of the contaminants. The combined assessment of ecotoxicity in water fractions, solubility and geochemical reactivity of PTEs in soils provided a more comprehensive understanding of the bioavailability of inorganic contaminants than ecotoxicological or chemical studies alone and can therefore be most useful for environmental risks assessment of contaminated soils.

Genetically determined resistance to lethal levels of copper by Daphnia longispina: Association with sublethal response and multiple/coresistance

The development of resistance to toxicants has been reported for a wide range of organisms. Two questions were addressed in the present study: Are genetically determined resistance responses at lethal levels (min to h) of copper associated with responses at extreme lethal (h to d) and sublethal levels and does genetically determined resistance to lethal levels of copper confer resistance to lethal levels of other chemicals? Twelve cloned lineages of Daphnia longispina, differing in their resistance to copper, were exposed to sublethal concentrations of copper and to lethal concentrations of copper, zinc, cadmium, hydrogen ions, and a pyrethroid insecticide (deltamethrin). Three kinds of toxicity assays were carried out: Survival time (death occurs in min to h; only for metals and hydrogen ions), cumulative mortality (death occurs in h to d; for all tested chemicals), and feeding depression assays (only for copper). A correlation between different levels of toxicity was observed only for extreme and moderate lethal responses to copper, and no correlation was found between lethal and sublethal levels of copper. Multiple resistance to lethal levels of toxicants was observed only for the pair copper/zinc.